6.

16
Functions Containing a Carbonyl
Group and Two Heteroatoms Other
Than a Halogen or Chalcogen
O. V. DENISKO
Chemical Abstracts Service, Columbus, OH, USA

6.16.1 FUNCTIONS CONTAINING AT LEAST ONE NITROGEN FUNCTION (AND NO

HALOGENS OR CHALCOGENS) 454
6.16.1.1 Carbonyl Derivatives with Two Nitrogen Functions 454
6.16.1.1.1 Reactions with isocyanates 454
6.16.1.1.2 Reactions with metal cyanates 460
6.16.1.1.3 Carbonylation of amines 460
6.16.1.1.4 Substitution reactions of amines with phosgene and its equivalents 461
6.16.1.1.5 Oxidation of thioureas and related compounds 466
6.16.1.1.6 Reactions of amines with amides and other carboxylic acid derivatives 466
6.16.1.1.7 Miscellaneous reactions 467
6.16.1.1.8 Preparation of carbamoyl azides 468
6.16.1.2 Carbonyl Derivatives with One Nitrogen and One P, As, Sb or Bi Function 468
6.16.1.2.1 Carbonyl derivatives with one nitrogen and one phosphorus(III) function 468
6.16.1.2.2 Carbonyl derivatives with one nitrogen and one phosphorus(V) function 469
6.16.1.2.3 Carbonyl derivatives with one nitrogen and one arsenic function (carbamoyl arsines) 470
6.16.1.2.4 Carbonyl derivatives with one nitrogen and one antimony function 471
6.16.1.2.5 Carbonyl derivatives with one nitrogen and one bismuth function 471
6.16.1.3 Carbonyl Derivatives with One Nitrogen and One Metalloid (B, Si, Ge) Function 471
6.16.1.3.1 Carbonyl derivatives with one nitrogen and one boron function 471
6.16.1.3.2 Carbonyl derivatives with one nitrogen function and one silicon function (carbamoyl silanes) 472
6.16.1.3.3 Carbonyl derivatives with one nitrogen and one germanium function (carbamoyl germanes) 473
6.16.1.4 Carbonyl Derivatives with One Nitrogen and One Metal Function 473
6.16.1.4.1 Carbon monoxide insertion reactions 473
6.16.1.4.2 Aminative carbonylation 474
6.16.1.4.3 Amination 474
6.16.1.4.4 Reactions with heterocumulenes (isocyanates, ketenimines, azides, carbodiimides) 475
6.16.1.4.5 Miscellaneous reactions 476
6.16.2 FUNCTIONS CONTAINING AT LEAST ONE PHOSPHORUS, ARSENIC, ANTIMONY,
OR BISMUTH FUNCTION (AND NO HALOGEN, CHALCOGEN, OR NITROGEN
FUNCTIONS) 476
6.16.2.1 Carbonyl Derivatives with Two P, As, Sb, or Bi Functions 476
6.16.2.2 Carbonyl Derivatives with One Phosphorus and One Metal Function 478
6.16.2.3 Carbonyl Derivatives with One B, As, Sb, or Bi Function, and One Metal Function 479
6.16.3 FUNCTIONS CONTAINING AT LEAST ONE METALLOID FUNCTION (AND
NO HALOGEN, CHALCOGEN, OR GROUP 5 ELEMENT FUNCTIONS) 479
6.16.3.1 Carbonyl Derivatives with Two Silicon Functions 479
6.16.3.2 Other Carbonyl Derivatives with Two Metalloid Functions 480
6.16.3.3 Carbonyl Derivatives with One Metalloid and One Metal Function 480
6.16.4 CARBONYL DERIVATIVES CONTAINING TWO METAL FUNCTIONS 481

453
454 Functions Containing a Carbonyl Group and Two Heteroatoms

6.16.1 FUNCTIONS CONTAINING AT LEAST ONE NITROGEN FUNCTION (AND NO

HALOGENS OR CHALCOGENS)

6.16.1.1 Carbonyl Derivatives with Two Nitrogen Functions

6.16.1.1.1 Reactions with isocyanates

(i) Additions of amines to isocyanates with formation of acyclic ureas

(a) Starting materials. The addition of various amines to isocyanates (Equation (1)) represents
the most widely used approach to the preparation of mono-, di-, and trisubstituted ureas and their
functionalized derivatives, especially if the starting isocyanates are readily available.
O
R1 R1 R2
N C O +
2 3
R R NH N N ð1Þ
H R3

As an amine component, ammonia <1994S56>, primary aliphatic amines <1999JOC2835,

2001MI351, 2003TL2065>, secondary aliphatic amines <2002PS(177)1303> and their silylated
<1996JGU349> and labeled <1993MI655> analogs, cycloalkyl <2001JCO171> and cycloalk-
enylamines <2001CPB391>, polyaza macrocycles <2001EJO1943>, hydroxyalkyl amines
<2001JMC2344, 2001MI191>, N-hydroxylamines <2000MI115723> and their O-alkyl deriva-
tives <1992BAU1920, 1996TL5835>, amino acids <1997TL4603, 2000TL1487>, allylic amines
<1993SC2065>, benzylic amines <1998TL1121, 1999JOC2835, 2000PHA490, 2003TL2065>,
arylamines <1996JMC1243, 1997SL1184, 1999JOC2835, 2003MI425>, heteroaryl amines
<1995JHC13, 2000BAU1202, 2001CPB391, 2001JCS(P1)2012, 2002CPB1379, 2002JMC2994>,
heterocyclic saturated <1996SC3685, 1997HCA966, 1998JCS(P1)3127, 2002HCA2458> and
partially hydrogenated amines <1992JHC1189, 2003SC1449>, azaheteroaromatics
<1995SL605>, heterocyclic ammonium and aminophosphonium salts <1993H(35)1237,
1994JOC7144, 2002JOC5527>, aminophosphonates <1993PS(85)161, 1994OPP357,
2002PS(177)1303>, diamines <2001PHA361, 2002MI81, 2002ZN(B)937, 2003JMC1112>, poly-
amines <1995CL759>, amino-substituted calixarenes <1995JOC6448, 2000MI1152,
2002T7207>, steroidal amines <2002OL4639>, amino sugars <1993T2655, 1993T2676,
2002SL1779>, nucleosides <1995BSB411>, amino borabicyclononanes <1992HAC245>, cyano
imines <2002JOC5546>, sulfimines <1999H(51)2035>, metalated acrylamides <2001JGU1953>,
N-arylsulfonyl sulfenamides <2001JOU1611>, sulfonamides <1994AP819, 1998EUP879816,
2001MI127, 2001MI404>, hydrazines <1994H(38)235, 1994JOC6487, 1996SC2941,
2001JMC1475, 2001MI42>, N-amino indoles <2001SL222>, hydrazides <1994AP469,
2000PHA490, 2001JMC1475, 2001MI180>, carbamates <1999TL6545>, isoureas
<1995AP393>, isothioureas <1996TL1945, 2002JCO285>, thiourethanes <1992JOU1635>,
guanidines <2002H(57)1799>, triazenes <2000JCO710>, and even amino ligands of organome-
tallic complexes <1994JOM(465)297> were used successfully.
Along with amines, isocyanates could also be used to introduce one or more functional groups
in the urea molecule. Due to the mild reaction conditions generally used, the reaction is tolerant
to a wide variety of functionalities, and urea preparation from ammonium isocyanate
<1993GEP4127562>, alicyclic <1995BSB411>, N-acyl <1993JGU1675, 1996SC2941> and unsa-
turated acyl isocyanates <1994H(38)235>, polyfluorinated <2000BAU1202>, polyunsaturated
<1994S56, 2003JOC5512>, azido- and diazine-substituted isocyanates <1993MI655>, glucosyl
and glucopyranosyl <1994SL919, 1995JCS(P1)377, 2000SL1253, 2001JOC4200, 2002SL1779>,
phosphoryl and thiophosphoryl isocyanates <1996JGU349>, radiolabeled <2002MI785>,
chlorinated <1992JOU1635, 2001MI351>, chlorosulfonyl <1996JHC943, 1996JMC1243>, aryl-
sulfonyl isocyanates <2001WOP23368>, and isocyanato-substituted carboranes <1996POL4355,
1997IC4753> has been reported.
Reaction of disubstituted silaazacyclohexanes with isocyanate-terminated polyurethane pre-
polymer afforded oligomeric silylureas useful as sealants <1994WOP14820>. The addition
of bulky 4-(triphenylmethyl)aniline to linear isocyanates at 40
C in the presence of a macrocyclic
host allowed for the preparation of nonpolymeric rotaxanes with urea-containing axles
<1997SL1184>.
 Functions Containing a Carbonyl Group and Two Heteroatoms 455

(b) Chemo-, regio-, and stereoselectivity of the addition. The chemoselectivity of the CuCl-
catalyzed carbamoylation of ergoline carboxamide 1 (Figure 1), bearing two reactive nitrogen
atoms is determined by the nature of the ligand used <1995SL605>. Thus, the best ligand
for carbamoylation of the indole nitrogen was found to be triethyl phosphite, whereas the
chemoselectivity was reversed in the presence of 2,20 -bipyridyl.

O H
N
H
NMe2
N
N H
H
1

Figure 1 Ergoline carboxamide: two reactive nitrogen atoms.

3-Amino-1H-1,2,4-triazole, also having two potential reaction sites, reacts with substituted
benzylic isocyanates exclusively at the ring nitrogen with the amino substituent remaining intact
<2002MI109>. A similar trend was observed on carbamoylation of 2-arylaminothiadiazolidinium
chloride <1993H(35)1237>.
2-Substituted 1-methylperhydropyrimidines 2 (R1 = Me, Et, i-Pr, Ph), existing in equilibrium
with minor, but more reactive open-chain tautomers, N-[3-(methylamino)propyl]imines,
react with isocyanates R2NCO (R2 = t-Bu, Ph, Bn) producing either ureas 3 or 4 (Scheme 1)
<1997HCA966>. The chemoselectivity depends mostly on the bulkiness of the R1 substituent with
smaller R1 substituents favoring the cyclic products 3.

R2NCO R2NCO
2
N N NHR N N R2HN N N
Me Me H Me
R1 O R1 O R1
3 2 4

Scheme 1

The reactions of isocyanates with
,-unsaturated amines bearing -hydrogen, such as 2,2-diamino
acrylonitriles <1994JHC329> or N-monosubstituted -aminovinyl trifluoromethyl ketones 5
(Scheme 2) <2000TL10141, 2003T1731>, give either C-addition products e.g., 6, or ureas e.g., 7,
with the nature of the predominating product depending both on the reactant substitution and
the reaction conditions. Generally, the increase in the steric hindrance caused by N-substituents or
those in the
-position to the amino group or higher reaction temperatures favor the formation of the
C-addition products, whereas the use of more polar solvents and addition of nucleophilic catalysts
(pyridine, triethylamine) shifts the equilibrium toward the ureas. The effect of isocyanate component
variation is less pronounced.

Ts Ts
O NH O NH
H TsNCO
H TsNCO N CF3 N CF3
N CF3 R 2
R2 1
R2
R O R1
R1 O O
6 5 7
R1 = H, Me, Ph;
R2 = H, Me, t-Bu, PhCH2, etc.

Scheme 2

The similar effect of the N-substituents was observed in reactions of acyl or phosphoryl
isocyanates with 2-amino-1-propenyl phosphonates <1993JGU1675>.
456 Functions Containing a Carbonyl Group and Two Heteroatoms

When optically active amines or isocyanates are used, the reaction proceeds without race-
mization affording optically active ureas and their derivatives <1994JOC6487, 2000M463,
2001JOC4200>.
(c) Experimental techniques and solid-phase synthesis. A series of 1,3-diaryl ureas was con-
veniently prepared in 80–93% yields by addition of anilines to 2-nitrophenyl isocyanate under
microwave irradiation conditions <2003MI425>. An automated solution-phase parallel synthesis
approach has been successfully implemented for the preparation of numerous urea libraries.
To eliminate the major problem of this approach, time-consuming work-up and purification,
a series of scavengers, both small-molecule and on a solid support, has been developed. Thus,
excess of an isocyanate could be effectively quenched using a fluoro-tagged primary amine
<1999JOC2835>, aminomethyl polystyrene <1998JCS(P1)3127> or microgel-supported
tris(2-aminoethyl)amine <2002JCO436> and removed from the reaction medium by simple
phase-separation or filtration, respectively. On the other side, the excess of an amine could be
readily removed with fluoroalkyl-substituted isatoic anhydride or isocyanate <2003TL2065>,
while the control over the unwanted amine presence could be carried out using ‘‘self-indicating’’
resins with pH-dependent color <2003JCO632>.
Lately, solid-phase synthesis has become the major approach to the preparation of urea
libraries and several procedures based on either the resin-bound isocyanate <1999TL2749,
1999TL4501, 2002MI81> or the resin-bound amine component <2000JCO710, 2001JCO189,
2001SL697, 2001TL1973, 2002JCO285, 2002OL597, 2002OL4033, 2003TL811> have been devel-
oped. m- and p-Ureido-substituted arylboronic acids were readily synthesized in 65–92% yields
and with >95% purity via the preliminary deactivation of the acid functionality by condensation
of an aminophenylboronic acid with resin-bound diethanolamine followed by treatment of the
polymer-supported boronate thus prepared with an isocyanate and mild acidic cleavage from the
solid support <2002JOC3>.

(ii) Additions of amines to isocyanates with formation of cyclic ureas

(a) Solution-phase reactions. Reactions of isocyanates with amines, bearing a suitably located
additional functional group sensitive to nucleophilic attack, are often followed by the intramolecular
reactions of the nitrogen atom of the newly formed urea fragment with formation of five- or
six-membered cyclic ureas. These ring closure reactions could be further subdivided into substitution
and addition reactions, the former being more widely exploited. This isocyanate addition/intramole-
cular substitution approach generally uses
- or -amino acids and esters as amine components,
and the ring closure step includes intramolecular acylation of the newly formed urea fragment (e.g.,
Scheme 3). This procedure is most commonly applied to the preparation of fused polyheterocyclic
systems <1993JHC897, 1993S111, 1994CPB2108, 1994JHC77, 1994JHC1569, 1994JOC1583,
1996TL5835, 1997WOP47626, 2002CPB1379, 2002JHC417, 2003JMC113>, but was also used
for the synthesis of monocyclic substituted tetrahydropyrimidinediones <2000TL4307>, chiral
hydantoins <2003OL2555>, and 5-alkoxyhydantoins <1997JOC3230>.

O
HO COOH HO COOH HO H
2
R2NCO N R
NHR2
NH N N
reflux N O
N N O
H R1 acetone/DMSO H R1 H R1
30–82% R1 = H, Me;
R2 = Me, Et, n-Pr, Ph

Scheme 3

Ethoxycarbonylhydrazones 8 of aromatic aldehydes and ketones react with 2 equiv. of

an isocyanate in triethylamine with formation of intermediates 9, which immediately undergo
intramolecular N-acylation/ring closure to give imino-substituted triazinetriones 10 (Scheme 4)
<1998JHC261>.
 Functions Containing a Carbonyl Group and Two Heteroatoms 457

EtO O O
R2 R3
H R3NCO (2 equiv.) 3 R1 N R3
N OEt N N NHR N N
R1 N N
Et3N, rt R2
O O O O N O
15–79% R1 R2
R3
8 9 10
R1 = Me, Ph, 4-ClC6H4, 4-MeC6H4;
R2 = H, Me

Scheme 4

On carbamoylation of 2-methylimidazoline, three equivalents of an aryl isocyanate are con-

sumed affording hexahydroimidazo[1,2-c]pyrimidine-5,7-diones in good yields <1994BAU1430>.
Intramolecular addition reactions, realized as a second step in one-pot preparation of cyclic
ureas, include: (a) addition to a carbonyl group <2003JOC754>; (b) addition to a thiocarbonyl
group followed by H2S elimination <2002HAC199>; (c) addition to a carboncarbon double
bond of enamines <1998S967>; (d) addition to a carbonnitrogen double bond of imines
<1998PHA607, 2001JCS(P1)1241>, isothiocyanates <1993IJC(B)779>, oximes <1999T475>,
diazo compounds <2002JMC5448> or methyleneamines, generated in situ by retro-Mannich
reaction of hexahydro-1,3,5-triazines <1995JHC995>; (e) addition to a carboncarbon
<1995JHC1141> or carbonnitrogen <2000PS(160)141, 2001EJO1695> triple bond. The latter
could further be followed by another cyclization reaction <1994AP469> or rearrangement
<2001JCS(P1)1241> thus providing access to highly substituted polyheterocyclic systems.
(b) Solid-phase synthesis. There are two major approaches to the solid-phase synthesis of
heterocycles with a urea fragment. The first is based on the direct construction of the desired
heterocyclic ring on the solid support using the isocyanate addition/cyclization procedures,
described above for solution-phase synthesis, followed by simple cleavage from the resin. The
representative examples of this approach include: preparation of quinazoline-2,4-diones from
resin-bound 2-aminobenzoates <1996TL4439>, 1,3-disubstituted uracils <2000TL1487> and
1,3,5-triazine-2,4,6-triones <2002JCO484> from
-amino esters, 1,3,5-triazine-2,4-diones from
resin-bound guanidines <2001JCO278>, and trisubstituted triazinobenzimidazolediones from
polymer-supported 2-iminobenzimidazoles <2002JCO345>.
In the second approach, the acyclic urea fragment is constructed while on a solid support.
The subsequent cleavage from the resin releases a reactive functional group (most commonly,
carboxylic group), which intramolecularly reacts with the nitrogen atom of the urea unit affording
the corresponding cyclic ureas. This approach was successfully used for synthesis of functionalized
hydantoins <1996TL5835, 1997TL4603, 1998MI129, 1999TL5841, 2000TL7409, 2001TL1973>,
spiro-hydantoins <2001JCO171>, tetrahydrouracils <1998MI139>, and 1,2,4-trisubstituted
urazoles <2002JCO491>.

(iii) Self-condensation and cycloaddition reactions of isocyanates

(a) Dimerization and trimerization reactions. Catalytic cyclodimerization and cyclotrimerization

reactions of isocyanates with formation of symmetrical 1,3-diazetidine-2,4-diones 11 or isocyanu-
rates 12, respectively, are well known (Scheme 5). The direction of the cyclocondensation depends
predominantly on the catalyst and the reaction conditions used.

O O
R R
N N
R N N R RNCO
O N O
O R
11 12

Scheme 5
458 Functions Containing a Carbonyl Group and Two Heteroatoms

A wide variety of catalysts for high-yielding trimerization of isocyanates includes fluoride

salts <1993JOC1932>, tricyclic proazaphosphatrane and its derivatives <1993AG(E)896,
1994JOC4931>, potassium or sodium piperidinedithiocarbamate under conventional or micro-
wave heating <2000JCR(S)145>, sodium p-toluenesulfinate <2002BCJ851>, trialkyl amines
<1994NKK146>, tetrasulfido tin complexes <1999OM4700>, and transition metal complexes
e.g., CpCo(PPh3)Me2, in supercritical carbon dioxide <2001JOM(626)227>. Even minor changes
in the catalyst composition can affect the product distribution: thus, self-condensation of PhNCO
in the presence of the oxoniobocene complex [Cp*2Nb(O)OMe] resulted in exclusive formation
of triphenyl isocyanurate, whereas the [Cp*2Nb(O)H]-catalyzed reaction gave a mixture of
dimerization and trimerization products with the former predominating <2001JOM(634)47>.
The exclusive or predominant formation of 1,3-diazetidine-2,4-diones 11 occurs either on
heating without a catalyst <2001JOU1747> or under catalysis with pyridine or 2- or 4-picolines
under high pressure <1994NKK146>. In the latter case, the selectivity of the dimerization
increases with the increase in pressure or in amount of the pyridine catalyst, whereas polar
solvents, such as acetonitrile, favor the trimeric product. The predominant dimerization of phenyl
isocyanate was also observed when 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU) was used as a
catalyst <1994JOC4931>.
The reaction of tungsten hexachloride with excess of ethyl isocyanate in dichloroethane led to
insertion of three isocyanate molecules into one of the tungstenchlorine bonds furnishing the
tungsten complex WCl4[(EtNCO)3Cl], which on hydrolysis gave isocyanurate 12 (R = Et)
<2002MI673>.
Self-condensation of isocyanates under aqueous (aq.) basic conditions affords acyclic symme-
trical ureas. Thus, heating 3-alkoxyphenyl isocyanates in aq. NaOH gave the corresponding
N,N0 -bis(3-alkoxyphenyl)ureas in 72–83% yields <1994CCC495>. Aromatic isocyanates were
readily converted into symmetrical 1,3-diaryl ureas in 85–95% yields in aq. pyridine at 20
C
<1999S1907>.
(b) Other cycloaddition reactions of isocyanates. SbCl5-Catalyzed 1,3-dipolar cycloaddition of
isocyanates with
-chloro-substituted azo compound 13 afforded the corresponding triazolonium
hexachloroantimonates 14 in moderate yields (Equation (2)) (where TMSNCO indicates
trimethylsilyl isocyanate) <1993T9973>, whereas 1,3-dipolar cycloaddition of isoquinolinium
arylimides, generated in situ from N-(arylamino)isoquinolinium halides, gave the corresponding
triazoloisoquinolones in 87–99% yields <1998EJO379>.

i. SbCl 5, CH2Cl2, Me + Me
Me N
Me –60 °C –
N R N N Ar SbCl6
Cl N Ar
ii. RNCO ð2Þ
42–68% O
13 14
Ar = 2,4,6-Cl3C6H2 R = H (from TMSNCO),
t-Bu, Ph

Heating phenyl isocyanate with nonsymmetrical azines 15 in xylene triggered two consecutive
1,3-dipolar cycloaddition reactions yielding heterocycles 16 with three fused five-membered
rings (Equation (3)) <2002TL6431>. 1,3-Dipolar cycloaddition of phenyl isocyanate to
-imino
thioamides occurs with sulfur elimination affording 4-amino-1,3-dihydroimidazol-2-ones
<1997BSF623>.

Ph O
OMe N
R
N
PhNCO Me N N
C N OMe
H2C Xylene Me ð3Þ
Me Me
Reflux R
15 16
R = Me (64%), Et (68%)

The in situ 1,3-dipole generation via thermal or palladium-catalyzed ring opening of three-
membered heterocycles, such as functionalized aziridines <1995JA4700, 2000JOC5887>, bicyclic
aziridines <2000SL1779>, or oxaziridines <2001TL9131>, in the presence of isocyanates
 Functions Containing a Carbonyl Group and Two Heteroatoms 459

presented a convenient method for regioselective preparation of substituted imidazolin-2-ones,

pyrazolo[1,2-a][1,2,4]triazolones and 1,2,4-oxadiazolidin-3-ones, respectively. A similar azetidine
ring opening/isocyanate cycloaddition of 2-vinyl azetidines under palladium catalysis
<2001SL914> or of 2-azabicyclo[2.2.0]hex-5-enes <2003JOC1626> afforded the corresponding
vinylic or azetidine-fused tetrahydropyrimidin-2-ones in moderate to excellent yields.
Chiral 2-alkenyl dihydrooxazoles 17 (X = O) react with 2 equiv. of aryl and arylsulfonyl isocyanates
to give nonracemic dihydropyrimidone derivatives 18 (Scheme 6) via asymmetric hetero-Diels–Alder
reaction followed by the addition of a second molecule of the isocyanate to the cycloadduct
<1997CC2311>. The thia analogs 18 (X = S) were obtained in the similar reactions of 17 (X = S)
with tosyl isocyanate; however, cycloaddition with less reactive phenyl isocyanate afforded 1:1 adduct
19 as the sole product <1999SL1379>.

R1 Ph
O R1
Ph
R3 N
R3HN N 2R3NCO PhNCO
X N S N O
X N O 25–94% (X = S, R1 = Ph,
R2 R2 = H)
R2
55% 19
18 17
X = O; R1 = Me, Et, Ph; R2 = Et;
X = S; R1 = Ph; R2 = H, (i-Pr)3SiOCH 2
R3 = Ph, 4-BrC6H4, Ts, etc.

Scheme 6

Other examples of hetero-Diels–Alder cycloaddition reactions with isocyanates include the

preparation of benzimidazolotriazinones and benzothiazolotriazinones from the corresponding
N-(2-heteroaryl) arylimines <1993SC1427> and of imidazo[5,1-d]-1,2,3,5-tetrazin-4-one
(temozolomide) and analogs from 5-diazoimidazole-4-carboxamide <1995JCS(P1)2783,
2002JMC5448>.
[2+2+2]-Cycloadditions of N-trimethylsilyl imine 20 with various isocyanates afforded
unsymmetrical 1,3,5-triazine-2,4-diones 21 (Scheme 7) in 75–96% yields <1995S1529>. Impor-
tantly, two different isocyanates could be added stepwise allowing for introduction of different
substituents on N-1 and N-3 atoms of the cycloadducts. Analogous [2+2+2]-cycloaddition
of 3-aryl-3,4-dihydroquinazolines with 2 equiv. of phenyl isocyanate gave the corresponding
quinazolinotriazinediones <2000EJO2105>.

CH2OTBDMS CH2OTBDMS CH2OTBDMS

CH2OTBDMS
R2NCO
R1NCO
R2
N N 75–96% HN N

TMS R1 R1 O N O
N N O O N
TMS TMS R1
20 21

Scheme 7

Benzotriazolyl-substituted iminium chloride undergoes [1+2+2]-cycloaddition with 2 equiv. of

phenyl isocyanate to give, after quenching with an appropriate nucleophile, functionalized
hydantoins in moderate yields <1996JHC1935>.
Conjugated heteroarylvinyl iminophosphoranes react with alkyl or phenyl isocyanates via the aza-
Wittig-type reaction and formation of carbodiimide intermediates to afford heteroarylmethylidene-
substituted imidazoline-2,4-diones in moderate yields <1994JOC6413>. A similar approach was used
for the solid-phase synthesis of 2-imino-4-oxo-1,3,5-triazino[1,2-a]benzimidazoles from resin-bound
2-benzimidazolyl iminophosphoranes <2003JCO155>.
460 Functions Containing a Carbonyl Group and Two Heteroatoms

6.16.1.1.2 Reactions with metal cyanates

Reactions of primary amines with sodium or potassium cyanates (Equation (4)) represent the most
common method for the preparation of monosubstituted ureas. As an amine component, benzylic amines
<2002JOC8827>, anilines <2000EJM879>, sterically constrained primary amines <1994TL8891>,

-amino acids <2001JCS(P2)1247, 2001MC32, 2002JOC8827>, -amino acids <2001MC32>, and
amino sugars <2002JCS(P1)1982> were successfully used. The kinetics of N-carbamoylation of

-amino acids with potassium cyanate were studied in detail <2001JCS(P2)1247>.
O
RNH2 + MOCN R ð4Þ
N NH2
(M = K, Na) H

Secondary aromatic amines <2003JOC754>, hydroxylamines <1994TL6017>, and even aza-

heterocycles, such as 4,5-disubstituted 2,4-dihydro-1,2,4-triazol-3-ones <1995GEP4343595>, were
also reacted with potassium cyanate to afford the corresponding urea derivatives. When the
amine component has a suitably located carbonyl group, the latter undergoes intramolecular
condensation with the newly formed urea fragment <2002JOC5527, 2003JOC754>.
The reaction of KOCN with haloalkyl acrylates and methacrylates 22 gave the corresponding
symmetrical ureas 23 (Equation (5)) <1993TL3857>. The presence of water is required to
suppress the trimerization of the intermediate isocyanates.

R R
KOCN O(CH2)nNH CO
O(CH2)nX H2C
H2C aq. MeCN
O O ð5Þ
Bu4 NBr 2

22 69–85% 23
R = H, Me; n = 6, 8; X = Cl, Br

Treatment of acyl or sulfenyl chlorides with silver cyanate in ether or aromatic solvents is
a convenient approach to in situ generation of isocyanates which are unstable and/or not
readily available. The subsequent addition of amines <1995TL6257>, N-alkoxyamines
<1995JHC1625>, or hydrazines <1995PHA379> allows for the preparation of the corresponding
functionalized ureas and sulfenyl carbazides.

6.16.1.1.3 Carbonylation of amines

A convenient approach to the conversion of primary and secondary amines into symmetrical
ureas is the catalytic oxidative carbonylation of the amines with CO/O2 (Equation (6)). A wide
variety of catalysts has been found effective for this reaction, including selenium compounds
<2000MI355, 2000USP6127575>, manganese-based catalysts <1993JCA631>, resin-immobilized
gold <2002JCA548>, Pd/H2SO4-modified ZrO2 <2001TL2161>, sulfur <1993HAC455>, polymer-
supported palladiumcopper catalyst <2000MI55>, PdI2/KI catalytic system <2003CC486>,
and palladium methoxycarbonyl complexes in the presence of CuCl2 <1994JOM(470)249>.
Electrocatalysis has also been applied <2001MI799>. Primary aromatic amines and secondary
aliphatic amines are generally less reactive than primary alkylamines, allowing for the prepara-
tion of unsymmetrical ureas by oxidative carbonylation of primary alkylamines in the presence
of excess of a less reactive amine <2001TL2161, 2003CC486>.
O
CO
R1R2NH + R3R4NH R1 R3
N N ð6Þ
Catalyst
R2 R4
or ∆

High-pressure Se-catalyzed carbonylation of amines and diamines with [11C] carbon monoxide
provided access to 11C-labeled cyclic and symmetrical acyclic ureas <2002JOC3687>. Treatment
of N,N0 -di(t-butyl)diaziridinone with Ni(CO)4 under CO atmosphere resulted in CO insertion into
the NN bond giving the ring expansion product, symmetrical N,N0 -di(t-butyl)diazetidinedione,
in 75% yield <1999H(50)67>.
 Functions Containing a Carbonyl Group and Two Heteroatoms 461

Instead of oxygen, iodine could be used as an oxidant. Thus, tungsten-catalyzed carbonylation

of aliphatic primary and secondary amines and diamines in the presence of iodine furnished
a series of acyclic <2000JMOC(A)11, 2000JOC5216> and cyclic ureas <1999OL961,
2002JOC4086, 2003JOC1615>. This reaction is compatible with acid-sensitive and fluoride-sensi-
tive functional groups. A nitroarene, such as 3-(trifluoromethyl)nitrobenzene, was also used as an
oxidant for Se-mediated conversion of primary alkylamines into symmetrical 1,3-dialkyl ureas
<1995JGU88>.
The ability of carbon monoxide to reduce nitroarenes to the corresponding anilines has been
exploited in the preparation of 1,3-diaryl- <1993USP5198582, 2002JCA255, 2003JMOC(A)135>
and 1-aryl-3-cycloalkyl ureas <2003JMOC(A)135>. Selenium is the most common catalyst for
this process, although a polymer-supported rhodium catalyst has also been applied
<2002JCA255>. In these reactions the nitro compound acts as both the reagent and an oxidant.
The use of toxic carbon monoxide could be avoided by replacing it with CO2. Thus, 1,3-dialkyl
ureas and 2-imidazolinones were successfully prepared from the corresponding amines or
diamines and CO2 at 80
C using the Ph3SbO/P4S10 catalytic system <1992JOC7339>. Trisub-
stituted ureas were also synthesized under these conditions in moderate yields, but the attempts
to prepare a tetrasubstituted urea, other than tetramethylurea, failed. This shortcoming was
later overcome by carrying out the reaction in the presence of carbon tetrachloride and
1,8-bis(dimethylamino)naphthalene <2002JOC9070>.
Purging CO2 into a mixture of a primary aromatic amine and DBU in pyridine or
tetrahydrofuran (THF) followed by addition of the trimethylamine–sulfur trioxide complex as a
dehydrating agent gave the corresponding 1,3-diaryl ureas in 23–87% yields <1995SC2467>.
The analogous reaction of ammonia with carbon dioxide with removal of water using
water-selective membranes allowed for the large-scale preparation of unsubstituted urea
<2001WOP04085>.
Heating primary aromatic or aliphatic amines with ethyl acetoacetate at 180
C in the
presence of the commercially available zeolite, HSZ-360, led to carbonylative dimerization of
the amines affording symmetrical 1,3-diaryl or 1,3-dialkyl ureas as the sole reaction products
<1998CC513, 1999JOC1004>. The reaction presumably occurs via the intermediate formation
of the corresponding acetoacetamide, which undergoes CC bond cleavage on further reaction
with an amine.

6.16.1.1.4 Substitution reactions of amines with phosgene and its equivalents

(i) Reactions of amines with phosgene

Despite its toxicity, phosgene is still utilized, although to a lesser degree than other carbonic acid
derivatives, for the conversion of amines into ureas (Equation (7)). The reaction generally takes
place in inert solvents (toluene, dichloromethane, THF) at 0–5
C in the presence of a base
(aq. NaHCO3, aq. NaOH, triethylamine, etc.).
O
R1R2NH + R3R4NH + COCl2 R1 R3 ð7Þ
N N
R2 R4

The reactions of phosgene with 2 equiv. of an amine were used for the synthesis of a variety
of symmetrical ureas, including N,N0 -carbonylbis(azoles) <1996EUP692476, 1997JOC4155,
2000GEP19830556, 2002GEP10035011> and cyclic ureas, such as 4,5-diaminoimidazol-2-ones
<1998EJO183>, imidazolidin-2-ones and their fused analogs <1993T4419>, tetrahydropyrimidin-
2-ones <2002HCA1999>, and hexahydroazepin-2-ones <1997JOC5380, 1998JOC9252>.
More useful, however, is the synthesis of unsymmetrical ureas by consecutive treatment of
phosgene with two different amines with in situ formation of an isocyanate intermediate.
A combination of two aromatic amines <2002WOP83642>, two amino acids <2001OL2313>,
or an aromatic or heterocyclic amine and O-alkyl hydroxylamine <1996TL2361, 2000CCA569>
were all successfully used. 14C-Labeled phenylureas bearing photoactive azido and diazine groups
were also prepared by this procedure <1993MI655>.
The reaction with phosgene was also employed in the solid-phase synthesis of functionalized
N-carbamoyl indolines <2000JA2966>.
462 Functions Containing a Carbonyl Group and Two Heteroatoms

(ii) Reactions of amines with carbamoyl chlorides

Reactions of carbamoyl chlorides with amines (Equation (8)) are comparatively seldom used for
the urea synthesis, probably due to a limited range of available carbamoyl chlorides.
O
R1 R3 ð8Þ
R1R2NH + R3R4NCOCl N N
R2 R4

Dialkyl and alkyl aryl carbamoyl chlorides were successfully used for carbamoylation
of azaheterocycles, such as triazoles <2002BCJ567>, oxazolidinones <2002JA9060> and
tetrazolinones <1995EUP646577>, arylhydrazines <1994S782>, and O,O0 -polyoxyethylene
bis(hydroxylamine)s <1993JOU1464>, the latter being dicarbamoylated. In contrast, treatment
of O,O0 -polyoxyethylene bis(hydroxylamine) with N-carbazolylcarbonyl chloride gave exclusively
the monocarbamoylation product, albeit in a moderate yield <2001SL682>.
Carbamoylation of pyridines affords the corresponding N-carbamoylpyridinium halides
<1996EUP692473>; however, when
-chloroformyl arylhydrazines 24 are used as the reac-
tants, further attack of the free amino group at the 2-position of the pyridine ring occurs to
afford [1,2,4]triazolo[4,3-a]pyridine-3-ones 25 (Equation (9)) <2001MI1135>. The analogous
cyclization reaction was observed with isoquinoline and pyridazine <2002MI239>. Pyrimidine,
however, was unreactive under the reaction conditions, whereas 1,3,5-triazine, thiazole, and
1,4,5,6-tetrahydropyrimidine underwent ring opening of the original heterocycle to afford
functionalized 2,4-dihydro-1,2,4-triazol-3-ones in good yields.
O
N
Ar 100 °C
N Cl + Ar N
N
NH2 N 12 h
O ð9Þ
excess 75–84%
24 25

Ar = Ph, 4-ClC6H4, 4-MeC6H4

Carbamoylation of N-alkyl hydroxylamines with N-cyano-N-arylcarbamoyl chlorides fol-

lowed by intramolecular addition of the N-hydroxy group to the nitrile furnished the corre-
sponding 1,2,4-oxadiazol-3-ones in 93–98% yields <2002SC803>. Analogous tandem
carbamoylation/intramolecular cyclization procedure was used for preparation of thiatetraazain-
denones and -fluorenones from mercapto-substituted triazoles and benzimidazoles, respectively
<2000M953>.

(iii) Reactions of amines with chloroformates

Chloroformates, bearing two good leaving groups of different nucleofugicity, represent conveni-
ent reagents for step-by-step CO-linking of different amines (Scheme 8) and preparation of
unsymmetrical ureas without isolation of the intermediate carbamates.

O O
O R4R5NH
1 2
R R NH + R1 R1 R4
N OR3 N N
Cl OR3
R2 R2 R5

Scheme 8

The most widely used are phenyl and 4-nitrophenyl chloroformates, although some alkyl
and chloroalkyl chloroformates are also applied. This approach was successfully used for the
preparation of di- and trisubstituted ureas <1996SC4253, 2002JAP(K)212160>, N-carbamoyl
amino esters <1996OPP173, 1997TL5335>, and N-arylcarbamoyl aminopyrazoles
<2002WOP66442> and indolines <2000SC1937>. The procedure was also applied to solid-
phase synthesis of functionalized ureas <1994TL4055, 1996TL4439>.
 Functions Containing a Carbonyl Group and Two Heteroatoms 463

When a substrate molecule has two amino groups of different reactivity, intramolecular
cyclization can occur. Thus, heating pyrazolyl hydrazides 26 with trichloromethyl chloroformate
gave pyrazolotriazinediones 27 (Equation (10)) <1999S453>, whereas condensation of

-hydrazono selenamide with methyl chloroformate afforded selenated 1,2,4-triazine-3-one in
49% yield <2000PS(164)161>.

R O Toluene N O
H + CCl3 N
N Cl O Reflux, 1 h NH
N Ar ð10Þ
N N 53–68% O N
H O H Ar
26 27
R = H, Cl, Br, NO2
Ar = Ph, 2-MeC6H4, 3-ClC6H4

(iv) Reactions of amines with carbamates and thiocarbamates

Carbamates represent the carbonic acid derivatives most widely used in the urea synthesis and
are generally prepared by partial aminolysis of chloroformates (see Scheme 8). O-Phenyl and O-t-
butyl carbamates are the most popular, the latter being readily available from amines
and (BOC)2O. Aminolysis of carbamates (Equation (11)) usually requires the presence of a base
(triethylamine, DBU, NaHCO3, etc.) and, when necessary, can be promoted by addition of
chlorosilanes <1998JOC8515, 2000JOC3239> or by heating over -Al2O3 <2000TL6347>.

O O
R3 R5 R1 R3
R1R2NH + N X N N ð11Þ
R4 R2 R4
X = O, S

The reaction is tolerant to a wide variety of the functional groups on both the carbamate and
the amine reactants allowing for the preparation of multiply functionalized ureas, including:
acryloyl ureas <1993EUP556841>, hydroxy-substituted ureas <1997S1189, 2001TL1445>,
polyfluorinated ureas <2000JOC1549>, arylsulfonyl <2001WOP05354> and heteroarylsulfonyl
ureas <1995WOP00509, 2001MI404>, carbamoyl diamino acids <1994EUP629612>,
N-carbamoyl nucleosides <1994HCA1267>, carbamoylamino glycosides <2000OL2113,
2001TL1445> and N-carbamoyl piperidines <1997S1189, 2000JOC1549>, piperazines
<1996SL507>, indolines <2001JHC451, 2002TL6649>, dihydroquinolines <2000TL6387>, and
dihydrophthalazines <2002JHC989>. The groups sensitive to the transformation include some
amino protecting groups, such as N-benzoate <2000MI405> and N-phenoxycarboxylate
<1992JOC5020>.
The carbamate aminolysis has also been applied to the solid-phase preparation of N-carbamoyl
dihydroquinolinones <2000SL45>, N-carbamoyl guanidines <1999JCO361>, oligoureas
<2000TL1553>, and libraries of di- and trisubstituted ureas <1998JOC4802, 2002MI81>.
On treatment with amines, cyclic carbamates, such as 2-oxazolidinones <1996TL1217> or
1H-thieno[2,3-d][1,3]oxazine-2,4-diones <1998T10789>, undergo aminative ring opening to
afford hydroxy- or carboxy-functionalized ureas, respectively.
When a reactive amino or imino function is already present in the carbamate or activated in situ by
deprotection, the intramolecular carbamoylation can occur allowing for access to variously substi-
tuted hydantoins <1997TL2065, 1998CC2703, 2000T3697>, optically active polycyclic ureas
<1996T8581>, triazinediones <2002HCO123>, and fused tetrazinones <2002JCS(P1)1877>.
Cyclic ureas could also be prepared by intermolecular carbamoylation if the carbamate and/
or amine component have additional reactive functional groups. Thus, hydantoins 29 (Equation (12))
and their dehydro derivatives were prepared by condensation of N-BOC amines 28 having the
464 Functions Containing a Carbonyl Group and Two Heteroatoms

activated
-position with imines <1996JOC428, 2001JOC2858, 2002EJO301> and nitriles

<1994JHC1689>, respectively. Cyclocondensation of
,-unsaturated -amino acids or their esters
with carbamates afforded uracil derivatives <1995JAP(K)0761975, 1998USP5817814>, whereas the
reaction of dihydrobenzodiazepinethione with ethyl carbazate gave fused triazolobenzodiazepinones
in moderate yields <2003JMC3758>. Pyrazolo[1,5-d][1,2,4]triazinones were prepared via the analo-
gous cyclocondensation of 5-acylpyrazolyl-1-carboxylates with phenylhydrazine <2002JOU602>.

R1 R3
1 OMe
R s-BuLi
+ N N
N R2
R3 N THF or Et2O OMe
R2 BOC O
–78 °C ð12Þ
28 29
22–92%
R1 = Ph, R2 = 4-MeOC6H4
R1 = benzotriazol-1-yl, R2 = PhCH2
R3 = Ph, 4-MeOC6H4, 2-furyl, etc.

Aminolysis of S-methyl alkylthiocarbamates with primary or secondary alkyl and cycloalkyl

amines in acetonitrile <1998TL3609>, or with primary sulfonamides in toluene in the presence of
DBU <2000SC3081>, gave the corresponding ureas and sulfonylureas in 60–89% yields without
racemization. Although benzamide and thiobenzamide were unreactive under these conditions,
aryl-substituted ureas were prepared in 81–100% yields by treatment of thiocarbamates with
generated in situ aniline carbanions <2000SC1675>.
Aminolysis of S-allyl N-acylthiocarbamates with a variety of amines in benzene-water two-
phase system <1993CCC575> or with phenylhydrazine in benzene <1993MI64> afforded the
corresponding acyl ureas and acyl semicarbazides, respectively.
Thermolysis of N-aryl carbamates at 230–240
C produces the corresponding symmetrical
1,3-diarylureas in 42–97% yields <1994RRC397>.

(v) Reactions of amines with ureas

(a) Preparation of acyclic ureas via disubstitution of symmetric ureas with amines. Microwave
irradiation of a mixture of an aromatic amine or phenylhydrazine with unsubstituted urea
afforded the corresponding symmetrical ureas in moderate-to-good yields (Equation (13))
<1999JCR(S)710>. The addition of a suitable energy-transfer solvent, such as N,N-dimethyl
acetamide, to the reaction mixture resulted in significant improvement in the product yields
<2000MI24>. Primary aliphatic amines <2000MI24> and 2-aminopyridines <2001HCO233>
reacted in a similar manner.

O Microwave O
RNH2 +
H2N NH2 40–90% RHN NHR ð13Þ
R = alkyl, aryl,
2-pyridyl, PhNH

However, of all the symmetrical ureas, commercially available, easily handled, crystalline
N,N0 -carbonyldiimidazole (CDI) is the most widely used as a phosgene equivalent. Significantly
lower reactivity of an N-carbamoylimidazole, formed after substitution of one imidazolyl
group with an amine, compared to CDI itself allows one to carry out the disubstitution
consecutively using two different amines or their analogs. This approach was applied
in the solution-phase synthesis of optically active dipeptides <1997TL5335, 2002JA9356>,
N-carbamoyltetrahydropapaverines <2002CPB1223> and 4-hydroxysemicarbazides
<2000HCO55, 2002HCO321>, and in the solid-phase synthesis of unsymmetrical polyfunctional
1,3-diaryl ureas <1997BOC277>.
Although N-carbamoyl imidazoles, formed from secondary amines and CDI, were found to be
unreactive toward coupling with secondary amines, these intermediates could be activated by their
conversion into the corresponding imidazolium salts <1998TL6267>, thus making this approach
suitable for the preparation of tetrasubstituted ureas.
 Functions Containing a Carbonyl Group and Two Heteroatoms 465

Instead of CDI, 1,10 -carbonylbis(benzotriazole) was used for preparation of tetrasubstituted

ureas (no activation is required in this case) <1997JOC4155> and for solution- and solid-phase
synthesis of dipeptides <1998TL7811>.
(b) Preparation of acyclic ureas via monosubstitution of ureas with amines. Condensation of
unsubstituted urea with a sterically hindered secondary amine in a strongly acidic medium
<2000CHE837> or with a heteroaromatic amine, such as pyrazole, under thermal conditions
<1992EUP508191> results in substitution of only one of the urea amino groups providing
products of the general formula R1R2NCONH2. On treatment of N-phenylurea with a variety
of amines, the unsubstituted amino group of the urea is cleaved, thus allowing access to a series of
1,3-di- and trisubstituted ureas <1992M607, 1995GEP4405056>. The same products could be
prepared by reaction of 1,3-diphenylurea with amines <1993OPP600>.
Analogously to the second step of the CDI aminolysis, reaction of independently prepared
N-carbamoyl imidazoles with amines leads to the substitution of the imidazolyl moiety with
the amino group <1994WOP06825>. Similarly, heating resin-bound 1-carbamoyl-1,2,3-benzotriazole
with primary or secondary amines results in the nucleophilic displacement of the benzotriazole
moiety releasing the newly formed unsymmetrical urea in the solution <2001JCO354>.
(c) Preparation of cyclic ureas. The most widely used procedure for the preparation of
cyclic ureas via the substitution pathway is the condensation of urea or its derivatives with
diamines. Unsubstituted urea or CDI are generally used as phosgene equivalents. This approach
was applied to the preparation of 2-imidazolidinones <1993T4419>, 2-benzimidazolones
<2002JCO320>, tetrahydropyrimidin-2-ones <2002HCA1999>, hexahydroazepin-2-ones
<1996USP5508400, 2002OL4673>, hexahydro-1,3,6-triazocin-2-one <1995EUP670316>, and
macrocyclic ureas <1993USP5206362>. A series of functionalized hydantoins were synthesized
from the corresponding resin-bound 1,2-diamines <1997TL931, 2001JCO68, 2002JCO175>.
Instead of two amino groups, their analogs, such as amide <1993TL7953>, hydrazine
<1999HCO473, 2001JHC1097>, or amidrazone <2002JMC2942> moieties, can participate in
the reaction.
If a second amine, used for the double aminolysis of CDI, features a suitably located carboxylic
group, the in situ intramolecular cyclization of the newly formed urea can occur giving, for
example, fused imidazolidinediones <1994JHC1235, 2002JHC417>. The similar intramolecular
cyclization after formation of the urea fragment was used for solution-phase <2000TL1159> and
solid-phase <2000TL1165> synthesis of 3-aminohydantoins and 3-aminodihydrouracils.

(vi) Reactions of amines with carbonates and thiocarbonates

(a) Preparation of acyclic ureas. Similarly to reactions of ureas with amines, aminolysis of
carbonates (Scheme 9) could be carried out by consecutive introduction of two different amines or
their analogs allowing for access to unsymmetrical ureas and their derivatives.

O O
O R4R5NH
R1R2NH + R1 R1 R4
N XR 3 N N
R3X XR3
R2 R2 R5
X = O, S

Scheme 9

Bis(trichloromethyl) carbonate, or triphosgene, is the most widely exploited. Using the coupling
reaction with triphosgene, ureas derived from two different amino acids <1994JOC1937,
1999TL2895>, as well as 1-aryl-3,3-dialkyl ureas <1998JCR(S)442>, glucopyranosylureas
<2001JOC4200>,
-ureido alkylphosphonates <2000PS(160)51, 2001JCR(S)470, 2001HAC68>,
carborane-substituted ureas <2000TL7065, 2001TL5913, 2002JOM(657)48>, ureapeptoid peptido-
mimetics <1997TL5335>, and urea-functionalized porphyrins <1998JOC2424> were all
successfully prepared. This approach has also been applied to the solution-phase synthesis of
tri- and tetrasubstituted ureas from polyethylene glycol-bound amines <2001BMCL271> and to
solid-phase synthesis of peptide C-terminal semicarbazones <1999TL6121>.
466 Functions Containing a Carbonyl Group and Two Heteroatoms

Other symmetrical carbonates, such as dimethyl carbonate <2002GC269>, diphenyl carbonate

<2001JAP(K)302640>, cyclic ethylene carbonate <1998EUP846679> and bis(1-cyclohexenyl)
carbonate <1995JAP(K)06239805>, as well as unsymmetrical diaryl carbonates <1996SC331>
were also used. Nitrophenyl carbonates were applied in the solid-phase synthesis of various ureas
<1998TL3631> and azapeptides <2000TL3983>.
Although di(t-butyl) carbonate is known to react with amines directly to give N-BOC-protected
derivatives, under catalysis with 4-(dimethylamino)pyridine (DMAP) it reacts with a second equivalent
of an amine to give the corresponding ureas. This procedure was successfully applied to primary aromatic
<1996SL502, 2000JOC6368>, primary aliphatic amines and resin-bound anilines <1999TL8563>;
however, with secondary amines only N-BOC protection was observed <2000JOC6368>.
The condensation of primary alkylamines with S,S-dimethyl dithiocarbonate in methanol or without
solvent at 60
C gave 1,3-dialkyl ureas <1996JOC4175>. Aromatic and sterically hindered alkylamines
are unreactive, whereas dialkylamines give only monosubstituted products i.e., thiocarbamates.
(b) Preparation of cyclic ureas. Condensation of carbonates with diamines leads to the
formation of cyclic ureas if the diamine structure allows for nonconstrained ring closure. This
procedure has been used for the preparation of benzimidazolones in solution <2001JCA91> and
on the solid support <1998TL179>, quinazoline-2,4-diones <2002M1067>, and macrocyclic
carborane-substituted ureas <2001TL5913>.
Low-valent titanium-induced carbonylative dimerization of aryl imines in the presence of
triphosgene gave substituted imidazolin-2-ones <2002SC2613>, which were also prepared via
DMAP-catalyzed carbonylative cyclization of 1,2-diamines with BOC2O <2000JOC6368>. Con-
densation of S,S-dimethyl dithiocarbonate with appropriate diamines afforded a series of imida-
zolin-2-ones, tetrahydropyrimidin-2-ones, and 2-quinazolinone in moderate to good yields
<1996JOC4175>.

6.16.1.1.5 Oxidation of thioureas and related compounds

Both acyclic and cyclic thioureas were readily converted into the corresponding ureas (Equation (14))
on treatment with bismuth nitrate pentahydrate in acetonitrile at reflux <2003TL591> or in
phosphate buffer at 20
C <2000MI285>. The reaction is chemoselective: although thioamides
are also oxidized, thiono esters and thioketones are essentially unreactive. Inexpensive, stable, and
commercially available Oxone could also be used as an oxidant <2003PS(178)61>; however, in
this case the excess of the reagent is required and a poorer chemoselectivity is observed.
S O
Oxidant
R1 R3 R1 R3 ð14Þ
N N N N
R2 R4 R2 R4

Oxidation of 1,3-di- and trisubstituted thioureas was also carried out using sodium metaper-
iodate, sodium chlorite, and ammonium persulfate in water <1997SC2357>, whereas N-aroyl
ureas were prepared via the oxidation of thioureas with bromine in chloroform (Hugershoff
reaction) <1994CCC2663>. Potassium iodate (KIO3) was found to be a convenient reagent for
the preparation of N-aroyl ureas <2000SC2635>, N-acylated bis(urea)s <2002SC3373>, and
N,N0 -diacyl semicarbazides <2000SC3405, 2000SC4543, 2001SC1433> from the corresponding
thiocarbonyl analogs. Trisubstituted glucopyranosyl thioureas were readily oxidized with excess of
yellow HgO <2002TL4313>; the disubstituted analogs, however, gave exclusively bicyclic isoureas.
There are few procedures specific for oxidation of cyclic thioureas. These include oxidation
with mercury(II) acetate, used for the preparation of 1,3-diacylimidazolidin-2-ones
<1993T4419>, and oxidation with 30% hydrogen peroxide in aq. NaOH, used in synthesis
of six-membered cyclic ureas <1994JHC1569, 1999JHC1327>. Tetrazolinethiones were oxidized
to tetrazolinones using unsubstituted oxirane or 2-alkyl epoxides as oxidants <1995EUP643049>.

6.16.1.1.6 Reactions of amines with amides and other carboxylic acid derivatives
Ruthenium-catalyzed carbamoylation of dialkylamines <1992USP5155267> or primary aromatic
amines <1997OM2562> with formanilides at 165
C give the corresponding unsymmetrical di-
and trisubstituted ureas in high yields. For reaction with anilines, unsubstituted formamide could
 Functions Containing a Carbonyl Group and Two Heteroatoms 467

also be used. Although simple alkyl and cycloalkyl amides are unreactive,
-polychloro- or

-polynitro-substituted aliphatic amides readily undergo -elimination to give intermediate isocya-
nates, which on trapping with ammonia or primary amines afford mono- and disubstituted ureas,
respectively (Scheme 10) <1992BAU891, 1994BAU821, 1994CL2299, 1994OPP357, 1999TL3235>.

O
O
∆ R3R4NH R2 R3
R2 R2NCO N N
R1 N
–R1H H R4
H

R1 = CCl3, O2NCCl2, MeC(NO2)2

Scheme 10

Curtius rearrangement of acyl azides also produces the intermediate isocyanates as urea
precursors. The starting acyl azides are usually generated in situ by one of the following methods:
(i) reaction of a carboxylic acid with diphenylphosphoryl azide in the presence of a base
<2001MI133, 2002MI109, 2002T4225>; (ii) from acyl chlorides and sodium azide <1999S943,
2000JHC1247>; or (iii) oxidation of acyl hydrazides with HNO2 <1998JCS(P1)2377>. This
approach has also been applied to the synthesis of N,N0 -disubstituted ureas from heterocyclic
and aliphatic carboxylic acids and resin-bound amines <2000OL3309>.

6.16.1.1.7 Miscellaneous reactions

(i) From carbodiimides

Hydrolysis of carbodiimides produces the corresponding ureas <2000CAR161>, whereas their hetero-
cyclization with diaryl nitrones <1998SC3665> or 2-(bromomethyl)acrylic acid <1996JHC1259> yields
polysubstituted 1,2,4-triazolin-3-ones and 5-methylidenetetrahydropyrimidine-2,4-diones, respectively.

(ii) Heterocycle ring–ring interconversions

Variously substituted 1,2,4-triazol-3-ones were prepared by ring opening/recyclization of
2-amino-1,3,4-oxadiazoles <2002JCR(S)213> or 5-amino-1,2,4-oxadiazoles (Equation (15))
<1996JOC8397> in the presence of a primary amine. The rearrangement of arylhydrazones
of 3-benzoyl-5-amino-1,2,4-oxadiazoles, however, occurs differently with formation of ureido-
substituted 1,2,3-triazoles <2002JOC8010>.
Ph H Ph
N hν N
N + R2NH2
R1 O O N
MeOH N ð15Þ
57–60% R2
R1 = NH2, NHMe, NMe2

R2 = H, Me, n-Pr, n-Bu, NH2

Heating 3-(2-oxopropyl)benzothiazol-2-ones with excess of a primary amine in HClO4 affords

1-(2-mercaptoaryl)imidazolin-2-ones, readily oxidizable in air to the corresponding disulfides
<2000PS(158)67>. Oxidative rearrangement of 3-arylimino-2-indolinones occurs with the ring
expansion to give quinazoline-2,4-diones <2000TL5265>.

(iii) Oxidation
Purines and xanthines are readily oxidized to the corresponding 8-oxo derivatives with dimethyl-
dioxirane <1995TL2665> or bacteria <1999JCS(P1)677>, whereas oxidation of benzimidazolium
salts and their N,N0 -polymethylene-bridged analogs in air affords the relevant benzimidazolones
468 Functions Containing a Carbonyl Group and Two Heteroatoms

in high yields <1994TL33, 1995TL2741>. Treatment of amidines with (diacetoxyiodo)benzene

yields either 1,3-disubstituted ureas or trisubstituted acylureas depending on the reaction condi-
tions <1997JCS(P1)2319>.

6.16.1.1.8 Preparation of carbamoyl azides

The early review on carbamoyl azides <1965CRV377> indicated three preparation methods,
which are still the ones most commonly used: (a) reaction of carbamoyl chlorides with
sodium azide; (b) addition of hydrazoic acids to isocyanates; and (c) oxidation of semicarbazides
with HNO2. Since this review, only few reports on synthesis of the title compounds have
appeared.
The reaction of carbamoyl chlorides with sodium azide usually occurs under very mild condi-
tions (aq. acetone, 0–20
C) with carbamoyl chlorides being used as such <1987GEP252824> or
prepared in situ from the corresponding amine and phosgene <1995JOC321>.
Treatment of chloroformyl <1985JOU1436> and
-chloroalkyl isocyanates <1976JOU1140>
with excess of hydrazoic acid resulted in both addition to the isocyanate moiety and substitution
of the chlorine atom with the azido group affording the corresponding diazido compounds,
whereas with -chloro-functionalized isocyanates no substitution reaction was observed
<1985RRC317>. The isocyanate reactant can also be generated in situ by addition of hydrazoic
acid to acyl ketenes accompanied by nitrogen elimination <1981JOC147, 1981JOC153> or by
Curtius rearrangement of acyl azides <1986JHC1103, 1990JOC5017>. Instead of unstable hydra-
zoic acid, its derivatives, such as trimethylsilyl azide <1980JOC5130> or triarylbismuth diazides
<1992JCR(S)34> could be used; however, in these reactions the mixtures of products are usually
obtained with the product distribution depending on the reaction conditions.
Other methods for synthesis of carbamoyl azides include oxidation of aldehydes with pyridi-
nium chloroformate in the presence of sodium azide <1988SC545> and reaction of carboxylic
acids with the Vilsmeier salt followed by treatment with sodium azide <1994TL2729>. The latter
approach is high-yielding and applicable to the preparation of a wide variety of carbamoyl azides,
including optically active substrates.

6.16.1.2 Carbonyl Derivatives with One Nitrogen and One P, As, Sb or Bi Function

6.16.1.2.1 Carbonyl derivatives with one nitrogen and one phosphorus(III) function
The most common procedure for the preparation of carbamoyl phosphines is based on the
phosphine addition to alkyl or aryl isocyanates (Equation (16)) <1995COFGT(6)499>. The
reaction is tolerant to the presence of thiol <1973JPR471>, alkylthio <1988JGU1310>, and
keto <1970JPR366> groups, and is applicable both to secondary and primary phosphines. In the
latter case, however, double carbamoylation of the phosphine occurs <1988JGU28>, even for
sterically hindered phosphines.

O
R1 R3
R1 R3 ð16Þ
P H + N C O P N
R2 R2 H

The bulky analog of PH3, tris(trimethylsilyl)phosphine (tris(TMS)phosphine), gives with iso-

propyl isocyanate exclusively 1:1 adduct 30, which exists in equilibrium with its (siloxy)imine
tautomer 31 (Equation (17)) <1989AG(E)53>. Under mild conditions, isocyanates readily insert
into the ZrP bond of PH-functionalized zirconocene complexes 32 to afford the corresponding
(phosphinoamidato)zirconocenes 33 in 81–85% yields (Equation (18)). The presence of a bulky
ligand, such as R1 = 5-C5EtMe4, favors the formation of complexes 33 exclusively as endo-
isomers (shown), whereas products 33 with less sterically hindered ligands e.g., R1 = 5-
C5MeH4, were formed as mixtures of endo- and exo-isomers, with exo-isomers predominating
<2000OM2445>. To our knowledge, up to the early 2000s, this reaction represents the only
procedure for the preparation of a secondary carbamoyl phosphine in acceptable yields.
 Functions Containing a Carbonyl Group and Two Heteroatoms 469

Pri Et2O, rt O OTMS

P(TMS)3 + N C O TMS Pri + TMS Pri
3 days P N P N ð17Þ
TMS TMS TMS
30 31

R1 O
Pentane, rt R1 Zr PHR2
[R12ZrCl(PHR2)] + R3NCO
24 h Cl N
R3
81–85% ð18Þ
32 R3 = i-Pr, Ph 33
R1 = (η5-C5EtMe4), R2 = cyclohexyl
R1 = (η5-C5MeH4), R2 = 2,4,6-Pr3i C6H2

The tertiary phosphine 34, bearing a suitably located boryl group, underwent addition to
phenyl isocyanate followed by intramolecular heterocyclization to give the six-membered hetero-
cycle 35 in 63% yield. On heating in benzene or acetonitrile, 35 readily rearranges to the bicyclic
heterocycle 36 (Scheme 11) <1991BAU2099>.

Bun
Ph Bun Ph Bun
Ph Bu C6H6, rt _ MeCN or C6H6 + _
+ Ph2P B Bun
+ PhNCO Ph2P BBu n2
Ph P BBun2 Overnight ∆ N
N
Ph O Ph
O Ph
34 35 36

Scheme 11

Another approach to the synthesis of tertiary carbamoyl phosphines, not including the reaction with
isocyanates, is based on carbamoylation of secondary phosphines with carbamoyl chlorides. The only
example of such a transformation, reported up to the early 2000s, is carbamoylation of bis(trimethyl-
siloxy)phosphine 37, which gave the desired derivatives 38 in moderate yields (Equation (19))
<1993JGU226>.
O
Et3N
(TMSO)2PH + ClCONR2 TMSO
Et2O P NR2
OTMS ð19Þ
rt, 2 days
37 38
52–61%
R = Me, Et; R2N = morpholino, piperidino

Phenylcarbamoyl phosphine 40 was obtained as the major product of hydrolysis of azaphos-

phaallene 39 (Equation (20)) <1990BCJ2736>. However, the hydrolysis pathway depends dra-
matically on the nitrogen substituent: for example, replacement of the phenyl group on
the nitrogen atom of 39 with a sterically hindered substituent, e.g., t-butyl, results in nucleophilic
attack at the phosphorus atom rather than at the carbon, giving quite different sets of products.
But
But But
H2O O
But P C N Ph Ph
P N ð20Þ
But But H H

39 40

6.16.1.2.2 Carbonyl derivatives with one nitrogen and one phosphorus(V) function
As in the synthesis of carbamoyl phosphines (Equation (16)), addition to isocyanates is the most
common procedure for the preparation of phosphorus(V)-bearing carbamoyl compounds. As
phosphorus reagents, both phosphine oxides <1983JHC331, 1991JGU622, 1995COFGT(6)499,
470 Functions Containing a Carbonyl Group and Two Heteroatoms

1996SC783, 2002HAC63> and trimethylsilylated phosphites (Equation (21)) <1987JMC1603,

1990T7175, 1995COFGT(6)499> can be utilized. The latter reaction was also applied to the
synthesis of chiral phosphorus dipeptides <1987JMC1603>. The isocyanate addition can be
followed by intramolecular heterocyclization to afford the corresponding phosphaazaheterocycles
<1995TL2021>. Diphosphanyl ketimine oxide 41 serves as a 1,3-dipole in [3+2]-cycloaddition
reaction with phenyl isocyanate resulting in formation of azaphospholene 42 in 75% yield
(Equation (22)) <2002CEJ3872>. The second, also widely used, approach is the substitution
reaction of alkoxycarbonyl or alkylthiocarbonyl phosphine oxides and phosphonates with nitro-
gen nucleophiles (Equation (23)). The reaction proceeds smoothly with ammonia
<1986JMC1389, 1995COFGT(6)499>, primary amines <1988JGU26, 1998SL1325>, amino
acids <1998SL1325> and diamines <2000HAC470>, and even with hydroxylamines
<1997JOC3858>, although in the latter case the reaction has to be carried out in pyridine to
avoid formation of the Lossen rearrangement product. A variety of functional groups, such as
alcohols, esters, or amides, is tolerated.
O
EtO OTMS CH2Cl2, rt
EtO R
P + RNCO P N
O
OEt OEt H ð21Þ

R = Ph, 87%
R = 4-O2NC6H4, 86%

Ph Ph Ph NPh
Ph
O P Toluene P
O
C C N Ph + PhNCO N Ph
Ph P reflux, 10 min Ph P ð22Þ
Ph Ph
75% O
41 42

O O
R3R4NH R1
R1
P NR3R4
P X R2 ð23Þ
R2 O O

X = OMe, SEt, OPh

P-Carbamoylation of 3-bis(siloxy)phosphinyl propanoate 43 under mild conditions with simul-

taneous elimination of TMSCl gave the functionalized carbamate 44 in 87% yield (Equation (24))
<1996JGU1867>.

O O
O
TMSO ClCONMe2 TMSO
P OTMS P OTMS
CH2Cl2 ð24Þ
OTMS O NMe2
reflux
43 44
87%

Studies on azide addition/Schmidt rearrangement of dialkyl acylphosphonates RCOPO(OR0 )2

revealed the formation of carbamoyl phosphonates RNHCOPO(OR0 )2 as the primary rearrange-
ment products <1994JA1016>. However, the yields of these compounds depend on the substitu-
tion in the starting acyl phosphonate and usually do not exceed 20%, making this approach
ineffective for the synthesis of carbamoyl phosphonates.

6.16.1.2.3 Carbonyl derivatives with one nitrogen and one arsenic function (carbamoyl arsines)
No information on the synthesis of tertiary carbamoyl arsines has been found in the literature.
The data on secondary carbamoyl arsines are essentially limited to the single early article
<1967LA248>, already reviewed <1995COFGT(6)499>, which reported the preparation of
these compounds via Sn-catalyzed addition of alkyl, cycloalkyl, and aryl arsines or their lithium
derivatives to phenyl or cyclohexyl isocyanates.
 Functions Containing a Carbonyl Group and Two Heteroatoms 471

The heterocycle 46, which could be considered as pyridine-fused cyclic carbamoyl arsine,
existing, however, exclusively in the hydroxy form shown (Scheme 12), was prepared in a low
yield by treatment of zwitterionic pyridooxadiazole 45 with tris(trimethylsilyl)arsine followed by
hydrolysis <1988TL3387>.

i. (TMS)3As, MeCN
18%
N + N As
O ii. MeOH, 2 h
N N
_ 82%
O OH
45 46

Scheme 12

6.16.1.2.4 Carbonyl derivatives with one nitrogen and one antimony function
No compounds of this type have been found in the literature.

6.16.1.2.5 Carbonyl derivatives with one nitrogen and one bismuth function
A single article, dealing with this class of compounds, reported the formation of quaternary
carbamoyl bismuthanes on treatment of dimethylformamide-BiCl3 adduct with tertiary amines
<1995COFGT(6)499>. To our knowledge, no more data on such compounds has appeared in the
literature since.

6.16.1.3 Carbonyl Derivatives with One Nitrogen and One Metalloid (B, Si, Ge) Function

6.16.1.3.1 Carbonyl derivatives with one nitrogen and one boron function
Carbamoyl boranes are generally prepared as adducts with tertiary amines, such as trialkyl
amines, pyridine, or quinuclidine, via two synthetic approaches based either on amidation of
amine-carboxyborane adducts or on hydrolysis of amine-cyanoboranes. Thus, direct coupling
of trimethylamine-carboxyborane 47 with primary or secondary aliphatic or primary aromatic
amines in the presence of the peptide-condensing agent dicyclohexylcarbodiimide (DCC) gave the
corresponding carbamoylborane adducts 48 in moderate yields (Equation (25)) <1987JCR(S)368,
1990BCJ3658, 1995COFGT(6)499>. A similar procedure was applied to the synthesis of the
boron analog of hydroxamic acid using hydroxylamine hydrochloride in water instead of an
amine <1988IC302>.
DCC
Me3N . BH2COOH + R1R2NH Me3N . BH2CONR1R2
CH2Cl2 ð25Þ
47 48
rt, 3 days
60–70%

The other general approach is based on a two-step procedure including addition of triethyl-
oxonium tetrafluoroborate to cyanoborane adducts followed by basic hydrolysis of the inter-
mediates 49 (Scheme 13).

– O
Et3O + BF 4 +– aq. NaOH
A . BHRCN A . RHB C N Et BF4 A . RHB NHEt
50–99%
49

Scheme 13
472 Functions Containing a Carbonyl Group and Two Heteroatoms

Both unsubstituted (R = H) <1990IC554, 1990IC3218, 1991T6915> and monosubstituted

(R = Me, i-Pr, i-Bu, s-Bu, Bn) cyanoboranes <1989CC900, 1989IS79, 1991IC1046> could be used,
whereas the second component (A) of the adduct could be a tertiary amine <1989CC900, 1990IC554,
1991IC1046>, triethyl phosphite <1991T6915>, or phosphonate <1990IC3218>. The similar treat-
ment of amine-dicyanoborane adduct afforded amine-bis(carbamoyl)boranes <1997CC1799>.
Limitation of the above method to the preparation of ethylcarbamoyl boranes due to exclusive
application of triethyloxonium tetrafluoroborate triggered a search for other synthetic proce-
dures, which up to the early 2000s have been represented by single examples. Thus, addition of
SbCl5 to Me3NBH2CN followed by treatment with t-butyl chloride and basic hydrolysis gives
t-butylcarbamoyl borane adduct <1994POL2599>.
Cyanation of diboratacyclohexane 50 with isonitrile 51 resulted in formation of the bridged salt
product, which on hydrolysis with aq. NaOH gave N-unsubstituted carbamoyl boracycle 52
(Scheme 14) <1991IC2228>.

Me H_ i. CHCl3 Me H_
+ + NH2
Me N B I + _ rt, 2 days Me N B
_ + Me3N.H2B–N C _
H B N+ H B
Me
ii. aq. NaOH N+ O
H Me H Me Me
80%
50 51 52

Scheme 14

Reaction of pyridine-cyanoborane adduct 53 (R = CN) (Figure 2) with methyl triflate at 40
C

in the absence of light gave the carbamoylborane adduct 53 (R = MeNHCO) in 19% yield
<2000S1229>. On stirring in methanol at room temperature (rt), the monomeric adduct of
triphenylborane with 2-(trimethylsiloxy)phenyl isocyanide undergoes dimerization/rearrangement
to afford heterocyclic diborane 54 in 20% yield <1996OM1251>.

Ph _Ph H OH _ O
_H H Cp*Cl3 Ta
+ B O B N SiMe3
S N R N+
+ +
N _O
S B
Ph Ph
53 54 58

Figure 2 Examples of carbamoyl boranes and silanes.

6.16.1.3.2 Carbonyl derivatives with one nitrogen function and one silicon function (carbamoyl silanes)
Since the early report on the preparation of the first thermally stable carbamoyl silane
Me3SiCONEt2 by silylation of dicarbamoyl mercury with hexamethyldisilathiane
<1995COFGT(6)499>, several approaches to the construction of the NCOSi link have been
developed, most of which, however, are applicable exclusively to tertiary carbamoyl silanes and
suffer from severe limitations. Up to the early 2000s unstable secondary carbamoyl silanes have
been prepared only by hydrosilylation of isocyanates either with t-BuPh2Li at 50
C
<1983T2989> or with Et3SiH in the presence of PdCl2 <1977JOM(140)97>.
Tertiary carbamoyl silanes 56, bearing a sterically hindered aryl group at the nitrogen atom,
have been prepared, albeit in low yields, via carbonylation of lithiated silyl amides 55, generated
in situ from the corresponding anilines and chlorosilanes, accompanied by 1,2-Si rearrangement
(Scheme 15) <1994OM1533>.

i. CO (30 atm.) O
Ar Li rt, 15 mi n
N Ar
N SiR3
SiR3 ii. MeI, –78 °C Me
55 17–40% 56
R3 = Me3, PhMe2
Ar =2,6-R′2C6H3 (R′ = Me, Et, i-Pr)

Scheme 15
 Functions Containing a Carbonyl Group and Two Heteroatoms 473

Silanes 56 could also be synthesized by sequential introduction of the carbonyl and trimethyl-
silyl group via carbonylation of mixed cuprates followed by silylation with a chlorosilane
<1994JOM(474)23>.
Lithiation/silylation of formamide HCON(Me)CH2OMe afforded the corresponding carbamoyl
silane Me3SiCON(Me)CH2OMe 57 in 61% yield <2001TL1423>. Although only the trimethylsilyl
(TMS) group could be directly introduced by this procedure, a series of carbamoyl silanes were prepared
via silyl group exchange by treatment of 57 with chlorosilanes at 145
C in the presence of CsF.
Although the synthesis of carbamoyl silanes by silylation of carbamoyl chlorides seems
obvious, the preparation of silanes (TMS)3SiC(O)NR2 (R = Me, Ph) from carbamoyl chlorides
R2NCOCl and (TMS)3SiLi(THF)3 still represent the only example of such a transformation
<1991JOM(403)293>.
Carbonylation of Cp*Cl3TaSiMe3 with limited quantities of CO followed by addition of pyridine
or 2,6-dimethylpyridine gives the stable Ta-carbamoyl silane complex e.g., 58 (Figure 2), bearing a
quaternary nitrogen atom <1989JA149>.

6.16.1.3.3 Carbonyl derivatives with one nitrogen and one germanium function (carbamoyl
germanes)
In contrast to the silicon analogs, only one example of synthesis of carbamoyl germanes using
trialkylgermyl chloride has been reported up to the early 2000s <1971AG(E)339>. All the other
known procedures use Et3GeLi as the germanium-introducing reagent. Thus, reaction of Et3GeLi
with CF3C(O)NEt2 <1983JOM(248)51> or Me3SiCCC(O)NMe2 <1984BAU1733> under
thermodynamic control conditions afforded carbamoyl germanes Et3GeC(O)NEt2 (56%) and
Et3GeC(O)NMe2 (45%), respectively.
The scope of the carbamoyl group-delivering reagents has been extended to carbamates
(Equation (26)) <1990POL227>. Me2NCOCl could also be used in this reaction as a carbamoyl-
ating reagent; however, in this case only 0.25 equiv. of the aluminum alkoxide should be employed
due to its rate-inhibiting effect.

O O
(sec-BuO)3Al (1 equiv.) N GeEt3
Et3GeLi + N OMe
X Hexane / benzene X ð26Þ
70–80 °C
X = O, 54%
3h X = CH2, 33%

6.16.1.4 Carbonyl Derivatives with One Nitrogen and One Metal Function

6.16.1.4.1 Carbon monoxide insertion reactions

One of the most widely used methods for the preparation of carbamoyl metal complexes is based on
the insertion of the carbon monoxide molecule into an already existing nitrogenmetal bond
(Equation (27)). The examples of organometallic compounds involved in the transformation include:
cuprates <1985JOM(297)379>, complexes of nickel <2002CC1840>, iron <1992JA1256>, platinum
<1985OM939>, palladium <2000OM1661>, rhodium <1988OM2234, 1992IC379>, iridium
<1994OM1751>, ruthenium <1993IC3640, 1999OM187>, rhenium <1998OM131>, molybdenum
<1987OM210>, tungsten <1986OM185>, thorium, and uranium <1988CRV1059,
1995COFGT(6)499>. Molybdenum or copper complexes containing more than one metalnitrogen
bond, such as Mo(NMe2)4 or lithium bis(amino)cuprates, undergo CO insertion into all these bonds
even under mild reaction conditions. In contrast, carbonylation of tungsten complex W2Cl2(NMe2)4
with excess of CO in toluene/pyridine gave exclusively the monoinsertion product in 69% yield
<1986OM185>.

O
CO ð27Þ
(L)n M NR2 (L)n M NR2
474 Functions Containing a Carbonyl Group and Two Heteroatoms

1,3-Dipolar cycloaddition reactions of (1,4-diaza-1,3-butadiene)tricarbonyliron complexes 59

(M = Fe) (Equation (28)) with electron-deficient alkynes, such as dimethyl acetylenedicarboxylate
(DMAD) or methyl propiolate, in the presence of an external ligand L [L = CO, P(OMe)3] is
accompanied by intramolecular insertion of a CO molecule into the metalnitrogen bond
affording thermally labile bicyclo[2.2.1] adducts 60 in 60–95% yields <1985OM948,
1986JOM(302)59, 1987JOM(323)67, 1990OM1691, 1996OM2148>.

R2
R
R
N CO N
M CO + R1 R2 + L
N
N CO O M R
R L ð28Þ
R1OC
CO
59 60

M = Fe, Ru R1 = R2 = CO2Me 60–95%

R = i-Pr, t-Bu R1 = H, R2 = CO 2Me

Analogous reactions of ruthenium complex 59 (M = Ru, R = i-Pr) with DMAD in the pre-
sence of CO or PPh3 as external ligands have been observed <1992OM3607>. In contrast to the
iron analogs, which are unreactive toward electron-deficient alkenes, ruthenium complexes 59
(M = Ru; R = Me, i-Pr) undergo cycloaddition with dimethyl maleate or fumarate to afford the
corresponding adducts in 70–90% yields <1995OM4781>.

6.16.1.4.2 Aminative carbonylation

Another widely used procedure for the preparation of carbamoyl metal compounds is based on
the introduction of both carbonyl and amine moieties into the organometallic compound and is
generally performed by carbonylation of a metal complex in the presence of a primary or a
secondary amine. Although most commonly used in the synthesis of platinum and palladium
carbamoyl compounds <1985JOM(296)435, 1987JOM(334)C9, 1990OM2603, 1990OM2612,
2000OM3879, 2002MI267>, this approach has also been applied to the preparation of carbamoyl
stannanes <1988JCS(P1)569>, nickel <1985AG(E)325, 1985JOM(281)379>, rhodium
<1993OM3410>, ruthenium <1998JOM(563)1>, and iron <2000OM3754> complexes.
A modification of this procedure includes carbonylation of metal complexes in the presence
of nitrobenzene as an amine precursor <2000OM3754, 2002MI267>; however, this reaction
requires significantly higher temperatures (80–160
C) compared to the one using amines (0
C–rt).
Indirect aminative carbonylation is represented by the reaction of Ph3PAuCl with methyl iso-
cyanide in aq. KOH, which afforded the unstable carbamoyl gold complex Ph3PAuC(O)NHMe,
presumably via hydrolysis of the intermediate isonitrile gold complex <1999IC3494>.

6.16.1.4.3 Amination
Currently, amination of metal carbonyl complexes represents the most common approach to the
preparation of metal carbamoyl derivatives and has been successfully applied to the synthesis
of carbamoyl complexes of Re <1988JOM(339)111, 1997JOM(541)423>, Mo <1989IC4414,
1991OM1305, 1997OM5595>, Ir <1992JOM(441)155>, Os <2002JOM(658)147, 2002MI963>,
Fe <1991IC1955, 1993OM1725, 1994CB711, 1996JCS(D)4431, 1997HCA121, 1999ZN(B)385,
2000OM15>, Mn <1991JOM(414)65>, Pd <1989OM2065, 1990JOM(383)587>, Ru
<1984IC4640, 1986ICA169, 1989JOM(368)103, 1989JOM(379)311, 2001OM3390>, Co
<1986OM2259, 1987CB379>, Cr <2001ZN(B)306>, W <1994OM1214, 1999OM748,
2001ZN(B)306>, and Pt <1985OM180, 1988JA7098, 1991OM175>. Both neutral metal com-
plexes (for Mo, Ir, Os, Pt, Mn, Ru, Fe) and cationic complexes (for Fe, Pd, Co, W, Pt, Re) could
be used. The reactions can be accompanied by the loss of a nonreacting ligand <2002MI963>.
As nitrogen nucleophiles, both primary <1991JOM(414)65, 1992JOM(441)155> and secondary
aliphatic amines <1988JA7098, 2002JOM(658)147>, cyclic amines <1988JOM(339)111,
1989JOM(368)103, 1990JOM(383)587>, aryl alkyl amines <1986ICA169>, anilines
 Functions Containing a Carbonyl Group and Two Heteroatoms 475

<1986OM2259>, amino esters <1999ZN(B)385>, hydrazines <1991IC1955, 1991OM1305> and

even N-substituted aziridines (with aziridine ring opening) <1997HCA121>, and N-nitrosoamines
<1993OM1725> were applied. An aromatic amine could also be generated in situ from the correspond-
ing nitroarene under reductive conditions <2001OM3390>.
In a metal complex with a ligand bearing a suitably located nucleophilic nitrogen atom,
intramolecular amination can occur <1990JOM(387)C5, 1996JCS(D)4431>. The outcome of
the reaction with diamines is determined by the starting organometallic compound: thus, cationic
(OC)5ReFBF3 reacts with both amino groups of diaminoalkanes in a standard fashion affording
the corresponding dicarbamoyl-bridged 2:1 complexes <1988JOM(339)111>, whereas monoami-
nation of (OC)5ReOSO2CF3 is followed by intramolecular attack of the second amino group at
the central metal atom with formation of the cyclic carbamoylrhenium complex
<1997JOM(541)423>.
Tetrakis(dimethylamino)methane, C(NMe2)4, has also been used as an efficient dimethylamino
group donor for the preparation of Ru <1984IC4640>, Cr and W <2001ZN(B)306> carbamoyl
complexes under mild conditions. The reaction proceeds via insertion of one of the carbonyls of the
metal carbonyl compound into the CN bond of the tetraaminomethane. A procedure based on a
similar mechanism was applied for the preparation of a series of bimetallic complexes. Thus, reaction
of carbonyl complexes M(CO)n (M = Fe, n = 5; M = Cr, Mo, W, n = 6) or Mn2(CO)10 with
organometallic dimethylamides, such as Al(NMe2)3 <1987JOM(323)149>, Ti(NMe2)4
<1993JOM(456)85>, Zr(NMe2)4 <2000JOM(598)403> or Cp*M0 (NMe2)3 (M0 = Ti, Zr)
<1995OM131>, gives the corresponding heterogeneous cluster compounds with M-CO-N fragment.

6.16.1.4.4 Reactions with heterocumulenes (isocyanates, ketenimines, azides, carbodiimides)

Reactions of neutral or cationic metal carbonyl complexes with isocyanates occur under mild
conditions (neutral solvents, rt) and result in formation of the corresponding metallacyclic 1:1
adducts with a cycle size depending on the central metal and on the nature and reactivity of
the ligands in the original complex. Thus, Cp2W(CO) gave four-membered metallacycles
<1987JA2173, 1989JA7424> and Cp2V(CO) yielded six-membered metallacycle
<1988JGU2384>, whereas five-membered metallacycles 62 (X = S) were obtained from cationic
Fe and Ru complexes 61 and isothiocyanates (Equation (29)) <1998JOM(568)241>. Analogous
reactions of the neutral complex (OC)2CpFePH(t-Bu) with isocyanates and isothiocyanates
provided 62 [X = O, S; R1 = t-Bu, R2 = R3NHC( = X)] <1998JOM(568)247>.

+ Cp R1
Cp R1 R3NCX M P
_ OC R2
OC M P R2 A t-BuOK O N X
OC H
toluene, rt R 3 ð29Þ
61 68–83% 62
M = Fe, Ru; X = S; A = BF4, PF6;
R1, R2 = i-Pr, t-Bu, Ph; R3 = Me, Et

This approach has also been applied to the preparation of cyclic carbamoyl mononuclear
manganese <1999OM2459>, cobalt <1991JOM(413)379>, iron <1987IC973> and binuclear
iron <1989OM443>, iridium <1988JA8543>, and rhenium <1999OM2459> complexes. Potas-
sium cyanate was utilized in the synthesis of five-membered carbamoyl platinacycle <1989G301>.
1,3-Cycloaddition of (5-MeC5H4)Mn(CO)2(THF) or Cp2Mo2(CO)4 with benzyl or aryl azides
gave the corresponding binuclear adducts e.g., 63 (Figure 3) <1986OM894, 1987OM2151>.
Cluster Os3(CO)11(NCMe) reacted similarly <1987OM2151>, whereas reactions of cobalt and
rhenium phosphine complexes CpM(CO)PR3 (M = Rh, R = i-Pr; M = Co, R = Me) occurred via
azide degradation followed by [2+1] cycloaddition to give metallaaziridinones 64 (R0 = Ph, Ts)
(Figure 3) in 69–79% yields <1992JOM(440)389>.
Metal carbonyl anions [CpFe(CO)2] and [Re(CO)5] undergo regiospecific [2+2] cycloaddi-
tion with ketenimines R1R2C¼C¼NR3 (R1 = R2 = Ph; R3 = Me, Ph) to give the isolable
anionic complexes e.g., 65 (Figure 3) <1985JOM(294)251>. Under similar conditions, the carbene
iron complex (CO)4Fe¼C(OEt)Ph afforded acyclic -allyl,-complexes 66 (R1 = Me, Et, i-Pr;
R2 = Me; R3 = Ph) <1991CB1795>.
476 Functions Containing a Carbonyl Group and Two Heteroatoms

Me _
Ph
OC Ph Ph
Mn Me Cp R2 CO2Et
N CO
Mn R3P M O
N (OC)4 Re N Ph
N R1 N R3
N CO (OC)3Fe
R′ O
O O
Ph
63 64 65 66

Figure 3 Carbamoyl metal complexes.

The reaction of Cp2W(CO) with diphenyl carbodiimide occurs by the same route as its reaction
with isocyanates to give [2+2]-cycloaddition product, imino-substituted metallaazetidinone, in 94%
yield <1989JA7424>. A similar formation of formal [2+2]-cycloaddition products was observed in
the reactions of CpW(CO)3H and Cp*W(CO)3H with acyclic or cyclic sulfur diimides
<1985ZN(B)1233, 1989JOM(371)303, 1993CB1781>. The reactions are regioselective: in the case
of monosubstituted sulfur diimides, only substituted nitrogen atom participates in the metallacycle
construction. When sulfur diimides with electron-accepting substituents, such as Ts, were used, no
cyclization was observed and only acyclic metalhydrogen bond insertion products were isolated.

6.16.1.4.5 Miscellaneous reactions

(i) Additions of metal carbonyls to iminophosphines and phosphine imides

Treatment of Fe or Mo carbonyl complexes with iminophosphines results in ligation of the
phosphorus to the metal atom followed by intramolecular attack of imine nitrogen at a CO ligand
to afford the corresponding metallaphosphaazetidinones <1985JA2553, 1986OM2376>. In con-
trast, the analogous reactions with phosphine imides are accompanied with the cleavage of the
phosphorusnitrogen bond giving metallapyrrolinone complexes in 69–72% yields <1991JA3800>.

(ii) Transmetallation
Platinum and palladium carbamoyl complexes (Et2NCO)M(PPh3)2X (M = Pt, Pd, X = Cl;
M = Pt, X = PPh3) were prepared in 75–87% yields by treatment of carbamoyl mercury com-
pounds ClHgCONEt2 or Hg(CONEt2)2 with Pt(0) or Pd(0) triphenylphosphine complexes at
20
C in benzene <1980BAU1490>.

(iii) Ligand modification reactions

Treatment of transition metal complexes bearing an alkoxycarbonyl ligand with primary aliphatic
or benzylic amines under mild conditions results in substitution of the alkoxy group with an
alkylamino fragment. The reaction was applied to the preparation of Ru <1994IC253>, Re
<1992IS211> and Fe <1985JCS(P1)2375, 1985T5871> carbamoyl complexes.

6.16.2 FUNCTIONS CONTAINING AT LEAST ONE PHOSPHORUS, ARSENIC,

ANTIMONY, OR BISMUTH FUNCTION (AND NO HALOGEN, CHALCOGEN,
OR NITROGEN FUNCTIONS)

6.16.2.1 Carbonyl Derivatives with Two P, As, Sb, or Bi Functions

One of the few approaches to the preparation of carbonyl compounds with two phosphorus
functions is based on the modification of the substituents on the central carbon of the already
existing PCP fragment. Thus, the parent carbonylbis(phosphonic) diacid was prepared in
 Functions Containing a Carbonyl Group and Two Heteroatoms 477

63% yield by basic hydrolysis of its dichloro derivative <1995COFGT(6)499>; however, this
procedure is restricted to this particular compound. Later, a series of carbonylbis(phosphonates)
68 (Equation (30)) was prepared by McKenna and co-workers by oxidation of the corresponding

-diazomethylenebis(phosphonate)s 67 with t-BuOCl. The product yields and formation of

,
-dichloro-substituted by-products depend on a solvent and the presence of water, with aq.
EtOAc being preferred as a solvent <1993PS(76)139, 1999PS(144)313, 2000WOP002889>.

N2 O
t-BuOCl O O
O O
P P P P
RO OR aq. EtOAc RO OR
OR OR OR OR
2–5 min ð30Þ
67 10–15 °C 68

R = Me (93%), Et (94%)
i-Pr (95%)

Another approach is based on the reaction of phosphines or their trimethylsilyl derivatives with
phosgene. In this reaction, the secondary phosphines give acyclic carbonyldiphosphines
<1995COFGT(6)499>, whereas primary phosphines and their silylated analogs afford four- or
five-membered phosphacycles (Scheme 16) <1983CB109, 1983TL2639, 1999ZAAC1979>, pre-
sumably via dimerization of phosphaketene intermediates.

O
COCl2 COCl2
Ph3CPH2 R P P R t-BuP(TMS)2
Et2O –60 °C
rt, 18 h O
94% R = t-Bu or Ph3C

Scheme 16

The formation of intermediate bis(phosphaketene) was also suggested for the preparation of
anionic heterocycle 69 (Figure 4) by treatment of PCOLi with SO2 in dimethoxyethane
(DME) at 50
C <1995ZAAC34>.

Me2P
PMe2
PMe2 P
Me2P P O
–O P C Th C
O Me2P O
P
P P P Me2P
PMe2
O P O– PMe2
69 70

Figure 4 Polycyclic phosphacarbonyl compounds.

Carbonylation of homoleptic eight-coordinated thorium dialkylphosphide

Th[P(CH2CH2PMe2)2]4 in hydrocarbons afforded the double insertion product 70 (Figure 4) in
73% yield <1994CC1249>. The similar carbonyl bridge formation between phosphorus ligands
was observed in reactions of sterically hindered (dialkylamino)dichlorophosphines with tetracar-
bonyl ferrate as the carbon monoxide source <1995COFGT(6)499>. The mechanism of this
transformation, steric requirements, and substituent effects have been studied in detail
<1990JOM(383)295>.
Organometallic compounds bearing a PCOP unit were also prepared via carbonylative PP
bond cleavage of metal diphosphine complexes. Thus, cleavage of the PP bond with insertion of
carbon monoxide was observed on treatment of iron complexes 71 or 72 with CO or excess
Fe2(CO)9 (Scheme 17) <1986ZN(B)283, 1991CB265> or by ring opening–ring closure of sub-
stituted cyclotetraphosphane in the presence of Fe2(CO)9 <1991CB265>.
478 Functions Containing a Carbonyl Group and Two Heteroatoms

O
But But CO t R But
R P Fe2(CO)9
P P P Bu P P
(OC)3Fe Fe(CO)3 Benzene (OC)3Fe Fe(CO)3 THF (OC)3Fe Fe(CO)3
80 °C, 20 h rt, 2 days
71 73 44% 72
75%
R = t-Bu, Cp*Fe(CO)2 R = Cp*Fe(CO)2

Scheme 17

Cleavage of the phosphorusphosphorus double bond followed by carbon monoxide insertion

on treatment of a series of Fe, Ru, or Os diphosphene complexes with excess of Fe2(CO)9 in
toluene affords the corresponding metallated diphosphinomethanone complexes, analogs of 73
<1986AG737, 1987CB1421>.
No information on the synthesis of carbonyl derivatives with two As, Sb, or Bi functions, or
unsymmetrical analogs has been found up to the early 2000s.

6.16.2.2 Carbonyl Derivatives with One Phosphorus and One Metal Function
The most important approaches to the preparation of carbonyl compounds with one phosphorus
and one metal function are based on: (a) carbon monoxide insertion into the metalphosphorus
bond; (b) formation of PCO bond via phosphinylation of metal carbonyls; (c) formation of the
MCO bond via reaction of metal complexes with
-keto phosphonates; and (d) carbonylative
phosphinylation of metal complexes.
The carbonylation approach has been successfully applied to the preparation of hafnium
<1988CRV1059, 1995COFGT(6)499>, thorium 70 (Figure 4) <1994CC1249>, and zirconium
complexes <1996OM1134> under mild conditions.
A series of phosphinocarbonyl complexes 75 was synthesized by reaction of cationic complexes
74 with the corresponding lithium phosphides (Equation (31)) <1985CB1193, 1985OM2097>.
The polarity of the reagent can also be reversed: thus, anionic bimetallic complex
(CpLi+)(CO)3MoCo(CO)4 readily reacted with chlorodiphenyl phosphine to give Mo2Co
product with a carbonyl bridge between phosphorus and cobalt atoms <2000JOM(607)156>.

O
_ –78 to 0 °C OC R1
[Cp*M(CO)3]+BF4 M P
+ LiPR1R2 OC
Et2O Cp* R2
30 min ð31Þ
74 75
M = Fe, Ru
R1, R2 = TMS, t-Bu

Neutral phosphines and phosphites were also applied for phosphinylation of carbonyl
complexes of molybdenum <1987OM1587>, iridium <1993JCS(D)1031>, and tantalum
<1987IC2556>.
Reaction of Ni(COD)2 with
-keto phosphonates in the presence of PPh3 affords 2-CO
coordinated complexes 76 (Equation (32)) <1990OM1958>.

O
Ph3P O
Ni(COD)2 + OMe PPh3
R P Ni OMe
OMe Et2O Ph3P R P
O OMe
rt O ð32Þ
76
R = Me (79%), Et (89%), Ph (73%),
4-ClC6H4 (65%), 4-MeC6H4 (72%)
 Functions Containing a Carbonyl Group and Two Heteroatoms 479

Treatment of Cp*Cl3TaSiMe3 with trialkyl phosphines or phosphites under CO atmosphere

results in carbonylative phosphinylation of the tantalum complex to give adducts 77 (Figure 5)
<1987IC2556, 1989JA149>, whereas carbonylation of zirconocenes bearing a phosphine-
functionalized cyclopentadiene ring affords intramolecular phosphinylation products 78
<1991OM2266, 1995OM1525>.

Cp*

_ O R2 R1 – Ru
C R2
Cp*Cl3 Ta C Zr O OC
SiMe3 Ru C
R3P + C Me R1
Cp*
R = Me, Et, OMe PPh 2
+
78 92
77
1 2
R = Cl, Me; R = H, PPh2 R = Me, Et; R2 = H, Me
1

Figure 5 Examples of carbonyl compounds with one phosphorus and one metal or two metal functions.

6.16.2.3 Carbonyl Derivatives with One B, As, Sb, or Bi Function, and One Metal Function
The reaction of 9-o- or 9-m-carboranecarbonyl chlorides with NaRe(CO)5 in THF at 70
C gave
the corresponding Re-complexes C2H2B10-CORe(CO)5 in 58–67% yields <1987BAU1486>.
The transmetallation of solvated lithium complex of arsadionate 79 using RuCl2(PPh3)3 in DME
afforded the Ru complex 80 with not fully delocalized arsadionate ligand (Equation (33))
<2001JCS(D)3219>. In contrast, the analogous reactions with FeCl2 or CoCl2 gave the complexes
with planar arsadionate ligands, coordinated to the metal center in a chelating 2-O,O-fashion.

But As But But As But

RuCl2(PPh3)3
O O O O
Li DME, –78 °C Ru
Li ð33Þ
O O Cl
73% PPh3
PPh3
But As But
79 80

No data on the preparation of carbonyl compounds with one Sb or Bi, and one metal function
have been reported up to the early 2000s.

6.16.3 FUNCTIONS CONTAINING AT LEAST ONE METALLOID FUNCTION (AND

NO HALOGEN, CHALCOGEN, OR GROUP 5 ELEMENT FUNCTIONS)

6.16.3.1 Carbonyl Derivatives with Two Silicon Functions

Two major approaches to the preparation of symmetrical bis(silyl) ketones involve C¼O bond
formation in the pre-existing SiCSi fragment and are based on oxidation and hydrolysis
reactions. Since the early synthesis of bis(triphenylsilyl) ketone via oxidation of the corresponding
alcohol <1995COFGT(6)499>, the efforts were concentrated mostly on the preparation of the
simplest representative of this class, bis(trimethylsilyl) ketone.
In the oxidative approach, (Me3Si)2CO 83 (Scheme 18) was readily prepared via ozonation of
bis(silylated) ylide 81 <1995COFGT(6)499, 1995LA415> or by oxidation of trimethylsilyl deri-
vative 82 with m-chloroperbenzoic acid (MCPBA) <1995COFGT(6)499>.

TMS O3 . P(OPh)3 TMS

MCPBA TMS SMe
C PPh3 O
TMS –78 °C TMS –78 °C TMS
TMS
Toluene CH2Cl2
81 83 82
30–50% 45%

Scheme 18
480 Functions Containing a Carbonyl Group and Two Heteroatoms

In the hydrolytic approach, preferred due to oxidizability of 83,
-halo ethers 85, prepared by
cleavage of O,S-acetal 84 with Br2 or SO2Cl2, readily hydrolyze on passing through a silica gel or
alumina column to afford TMS2CO in 65–75% yields (Scheme 19) <1998ACS1141,
1998SC1415>.

TMS Br2 or SO2Cl2 TMS Silica gel TMS

TMS TMS O
pentane
PhS OMe CH2Cl2 X OMe TMS
ether
84 85 75–78% 83
X = Cl (65%)
X = Br (82%)

Scheme 19

Similarly, bis(silyl)bis(methylthio) ketone 86, obtained by double lithiation/silylation of

bis(methylthio)methane, undergoes hydrolysis on treatment with HgOBF3  Et2O to give
bis(dimethylphenylsilyl) ketone (Equation (34)) <1990CL1411>.

MeS SMe HgO-BF3.Et2O O

PhMe2Si 56% PhMe2Si SiMe2Ph ð34Þ

SiMe2Ph
86

To our knowledge, no isolable unsymmetrical bis(silyl)ketones have been synthesized up to the

early 2000s, although the formation of (trimethylsilyl)(triphenylsilyl) ketone on hydrolysis of the
corresponding 2,2-disilylated 1,3-dithiane was proposed on the basis of infrared spectra
<1968CJC2119>.

6.16.3.2 Other Carbonyl Derivatives with Two Metalloid Functions

The first bis(germyl) ketone, Et3GeCOGeEt3, was prepared via neutral hydrolysis of the corre-
sponding 2,2-digermyl 1,3-dithiane derivative and characterized in solution <1967JA431>. One
year later, bis(triphenylgermyl) ketone was prepared in 73% yield by oxidation of the correspond-
ing alcohol and fully characterized <1968CJC2119>. Since then, only one procedure for the
preparation of these compounds has been reported: bis(trimethylgermyl) ketone 89 (M = Ge) was
synthesized via germylation of thioacetal 87 followed by halogenation of 88 with SO2Cl2 and mild
hydrolysis of the intermediate
-chloro ether on silica gel (Scheme 20) <2000JCS(P1)2677>.
Mixed (trimethylsilyl)(trimethylgermyl) ketone 89 (M = Si) was prepared similarly (Scheme 20).
No data on synthesis of other carbonyl compounds with two metalloid functions have been found
up to the early 2000s.

i. t-BuLi, THF i. SO 2Cl2, CH2Cl2

GeMe3 GeMe3 O
–78 °C Me3M 0 °C, 30 min
PhS OMe ii. Me 3MX PhS OMeii. Cyclohexene Me3M GeMe3

87 THF, –78 °C 88 0 °C, 30 min 89

M = Si, X = Cl, 90% iii. Silica gel M = Si, 53%
M = Ge, X = Br, 92% pentane M = Ge, 65%

Scheme 20

6.16.3.3 Carbonyl Derivatives with One Metalloid and One Metal Function
The most general approach to the preparation of the silaacyl metal compounds is based in the
insertion of carbon monoxide into the metalsilicon bond. Thus, carbonylation of silyl zirconium
complexes 90 gives 2-silaacyl complexes 91 (Equation (35)) <1988CRV1059, 1988JOM(358)169,
1995COFGT(6)499>.
 Functions Containing a Carbonyl Group and Two Heteroatoms 481

R2 Cp
Cp CO (100 psi)
R2 Zr SiR33
Zr rt R1
R1 SiR33
pentane or Et2O O ð35Þ
90 91
71–90%
R1 = Cp, Cp*; R2 = Cl, TMS
R3 = Me, TMS

Analogous products, prepared from complexes bearing disubstituted silyl moiety, have been
found to be unstable <1989OM324>. A similar procedure was applied for the preparation of
2-silaacyl complexes of Re <1995COFGT(6)499>, Ta <1989JA149, 2002OM3108>, and Fe
<1992T7629>. In the latter case Fe2(CO)9 was used as a carbon monoxide source.
No information on the synthesis of other carbonyl compounds with one metalloid and one
metal function has been found up to the early 2000s.

6.16.4 CARBONYL DERIVATIVES CONTAINING TWO METAL FUNCTIONS

Detailed information on both homonuclear and heteronuclear polymetallic clusters with a CO
bridging ligand can be found in the appropriate volumes of Comprehensive Organometallic
Chemistry-II <1995COMCII> and in a series of yearly reviews titled ‘‘Organo-Transition Metal
Cluster Compounds’’, published in Organometallic Chemistry e.g., <2000MI275>, so the follow-
ing survey is intended to give only a brief summary of the methods used for the preparation of
title compounds in the period 1994–2003.
One of the most widely used approaches for the preparation of homonuclear bimetallic clusters
with a CO bridging ligand is based on reductive carbonylation of the corresponding metal halides
in ethylene glycol <1999JOM(580)117, 2003JOM(669)44>, or on the surface of inorganic oxides
or zeolites <2003CRV3707>, or carbonylation of neutral metal complexes <2002IS210>. Enals,
such as crotonaldehyde or 2-pentenal, could serve as a source of bridging CO: thus, treatment of
[Cp*RuCl]4 with these enals in the presence of K2CO3 gave diruthenium complexes 92 (Figure 5) in
36–65% yields <1994OM2423>.
Other dirhodium and dirhenium clusters were obtained by dimerization of the corresponding
monomeric rhodium and rhenium carbonyls at room temperature or on heating
<1999JOM(577)167, 2001IC2979>. Dimerization of indenyl rhenium tricarbonyl under UV
irradiation was accompanied by loss of one CO ligand <1999OM1353>.
Another approach, applied to the preparation of both homonuclear and heteronuclear bime-
tallic CO-bridged complexes, includes reaction of metalmetal bonded carbonyl compounds with
external ligands, such as PPh3 <2000EJI159>, acetonitrile <2002JOM(658)117>, or alkynes
<1994OM4695, 1995AJC1651, 2002OM4847>, which force one of CO ligands to change
its binding mode. Similarly, the reaction of iron carbonyls with t-BuGeH3 <1994CL293> or
Cp*2GaCl <2002JOM(646)247> yielded ironiron bonded complexes containing both -germyl-
ene or -gallium and -CO bridges.
A similar procedure was applied to the preparation of heteronuclear clusters, such as CO-
bridged RuPd <2002JA5628>, IrMo, IrW, IrFe <2002ICA204>, FeRe, and FeMn
complexes <1998OM2945, 2000OM72>.

REFERENCES
1965CRV377 E. Lieber, R. L. Minnis, Jr., C. N. R. Rao, Chem. Rev. 1965, 65, 377–384.
1967JA431 A. G. Brook, J. M. Duff, P. F. Jones, N. R. Davis, J. Am. Chem. Soc. 1967, 89, 431–434.
1967LA248 A. Tzschach, R. Schwarzer, Liebigs Ann. Chem. 1967, 709, 248–256.
1968CJC2119 A. G. Brook, P. F. Jones, G. J. D. Peddle, Can. J. Chem. 1968, 46, 2119–2127.
1970JPR366 K. Issleib, P. von Malotki, J. Prakt. Chem. 1970, 312, 366–377.
1971AG(E)339 P. Jutzi, F.-W. Schröder, Angew. Chem., Int. Ed. Engl. 1971, 10, 339.
1973JPR471 K. Issleib, K. D. Franze, J. Prakt. Chem. 1973, 315, 471–482.
1976JOU1140 O. V. Vishnevskii, L. M. Trikhleb, L. I. Samarai, J. Org. Chem. USSR (Engl. Transl.) 1976, 12,
1140.
1977JOM(140)97 I. Ojima, S.-I. Inaba, J. Organomet. Chem. 1977, 140, 97–111.
1980BAU1490 V. I. Sokolov, G. Z. Suleimanov, A. A. Musaev, O. A. Reutov, Bull. Acad. Sci. USSR, Div. Chem.
Sci. (Engl. Transl.) 1980, 29, 1490–1493.
1980JOC5130 O. Tsuge, S. Urano, K. Oe, J. Org. Chem. 1980, 45, 5130–5136.
482 Functions Containing a Carbonyl Group and Two Heteroatoms

1981JOC147 D. C. England, J. Org. Chem. 1981, 46, 147–153.

1981JOC153 D. C. England, J. Org. Chem. 1981, 46, 153–157.
1983CB109 R. Appel, W. Paulen, Chem. Ber. 1983, 116, 109–113.
1983JHC331 G. M. Coppola, J. Heterocycl. Chem. 1983, 20, 331–339.
1983JOM(248)51 D. A. Bravo-Zhivotovskii, S. D. Pigarev, I. D. Kalikhman, O. A. Vyazankina, N. S. Vyazankin, J.
Organomet. Chem. 1983, 248, 51–60.
1983T2989 J. E. Baldwin, A. E. Derome, P. D. Riordan, Tetrahedron 1983, 39, 2989–2994.
1983TL2639 R. Appel, W. Paulen, Tetrahedron Lett. 1983, 24, 2639–2642.
1984BAU1733 D. A. Bravo-Zhivotovskii, S. D. Pigarev, O. A. Vyazankina, A. S. Medvedeva, L. P. Safronova,
N. S. Vyazankin, Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1984, 33, 1733–1734.
1984IC4640 A. Mayr, Y. C. Lin, N. M. Boag, C. E. Kampe, C. B. Knobler, H. D. Kaesz, Inorg. Chem. 1984, 23,
4640–4645.
1985AG(E)325 H. Hoberg, F. J. Fañanás, Angew. Chem., Int. Ed. Engl. 1985, 24, 325.
1985CB1193 L. Weber, K. Reizig, R. Boese, Chem. Ber. 1985, 118, 1193–1203.
1985JA2553 A. M. Arif, A. H. Cowley, M. Pakulski, J. Am. Chem. Soc. 1985, 107, 2553–2554.
1985JCS(P1)2375 S. T. Hodgson, D. M. Hollinshead, S. V. Ley, C. M. R. Low, D. J. Williams, J. Chem. Soc., Perkin
Trans. 1 1985, 2375–2381.
1985JOM(281)379 H. Hoberg, F. J. Fañanás, K. Angermund, C. Krüger, M. J. Romão, J. Organomet. Chem. 1985,
281, 379–388.
1985JOM(294)251 W. P. Fehlhammer, P. Hirschmann, A. Völkl, J. Organomet. Chem. 1985, 294, 251–260.
1985JOM(296)435 G. Vasapollo, C. F. Nobile, A. Sacco, J. Organomet. Chem. 1985, 296, 435–441.
1985JOM(297)379 Y. Wakita, S.-Y. Noma, M. Maeda, M. Kojima, J. Organomet. Chem. 1985, 297, 379–390.
1985JOU1436 M. N. Gertsyuk, L. I. Samarai, J. Org. Chem. USSR (Engl. Transl.) 1985, 21, 1436.
1985OM180 M. A. Bennett, A. Rokicki, Organometallics 1985, 4, 180–187.
1985OM939 H. E. Bryndza, W. C. Fultz, W. Tam, Organometallics 1985, 4, 939–940.
1985OM948 H.-W. Frühauf, F. Seils, R. J. Goddard, M. J. Romão, Organometallics 1985, 4, 948–949.
1985OM2097 L. Weber, K. Reizig, R. Boese, Organometallics 1985, 4, 2097–2101.
1985RRC317 I. Baracu, E. Tărnăuceanu, V. Dobre, I. Niculescu-Duvăs, Rev. Roum. Chim. 1985, 30, 317–327.
1985T5871 S. T. Hodgson, D. M. Hollinshead, S. V. Ley, Tetrahedron 1985, 41, 5871–5878.
1985ZN(B)1233 M. Herberhold, W. Jellen, W. Bühlmeyer, W. Ehrenreich, Z. Naturforsch., Teil B 1985, 40,
1233–1236.
1986AG737 L. Weber, K. Reizig, R. Boese, Angew. Chem. 1986, 98, 737–739.
1986ICA169 M. Nonoyama, Inorg. Chim. Acta 1986, 115, 169–172.
1986JHC1103 C. Galvez, F. Garcia, J. Garcia, J. Soldevila, J. Heterocycl. Chem. 1986, 23, 1103–1108.
1986JMC1389 M. M. Vaghefi, P. A. McKernan, R. K. Robins, J. Med. Chem. 1986, 29, 1389–1393.
1986JOM(302)59 H.-W. Frühauf, F. Seils, J. Organomet. Chem. 1986, 302, 59–64.
1986OM185 K. J. Ahmed, M. H. Chisholm, Organometallics 1986, 5, 185–189.
1986OM894 G. D. Williams, G. L. Geoffroy, A. L. Rheingold, Organometallics 1986, 5, 894–898.
1986OM2259 Q.-B. Bao, A. L. Rheingold, T. B. Brill, Organometallics 1986, 5, 2259–2265.
1986OM2376 D. Gudat, E. Niecke, B. Krebs, M. Dartmann, Organometallics 1986, 5, 2376–2377.
1986ZN(B)283 R. L. De, D. Wolters, H. Vahrenkamp, Z. Naturforsch., Teil B 1986, 41, 283–291.
1987BAU1486 L. I. Zakharkin, V. A. Ol’shevskaya, Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1987,
36, 1486–1487.
1987CB379 H. Werner, L. Hofmann, R. Zolk, Chem. Ber. 1987, 120, 379–385.
1987CB1421 L. Weber, K. Reizig, D. Bungardt, R. Boese, Chem. Ber. 1987, 120, 1421–1426.
1987GEP252824 H. W. Abraham, K. Dreher, E. Rehak, D. Kreysig, Ger. Pat. (East) DD 252,824 (1987) (Chem.
Abstr. 1988, 109, 190459).
1987IC973 L. K. Johnson, R. J. Angelici, Inorg. Chem. 1987, 26, 973–976.
1987IC2556 J. Arnold, T. D. Tilley, A. L. Rheingold, S. J. Geib, Inorg. Chem. 1987, 26, 2556–2559.
1987JA2173 P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1987, 109, 2173–2174.
1987JCR(S)368 M. K. Das, P. Mukherjee, J. Chem. Res. (S) 1987, 368.
1987JMC1603 P. P. Giannousis, P. A. Bartlett, J. Med. Chem. 1987, 30, 1603–1609.
1987JOM(323)67 H.-W. Frühauf, F. Seils, J. Organomet. Chem. 1987, 323, 67–76.
1987JOM(323)149 J. Fr. Janik, E. N. Duesler, R. T. Paine, J. Organomet. Chem. 1987, 323, 149–160.
1987JOM(334)C9 F. Ozawa, L. Huang, A. Yamamoto, J. Organomet. Chem. 1987, 334, C9–C13.
1987OM210 M. H. Chisholm, C. E. Hammond, J. C. Huffman, Organometallics 1987, 6, 210–211.
1987OM1587 P. V. Bonnessen, P. K. L. Yau, W. H. Hersh, Organometallics 1987, 6, 1587–1590.
1987OM2151 M. D. Curtis, J. J. D’Errico, W. M. Butler, Organometallics 1987, 6, 2151–2157.
1988CRV1059 L. D. Durfree, I. P. Rothwell, Chem. Rev. 1988, 88, 1059–1079.
1988IC302 V. M. Norwood III, K. W. Morse, Inorg. Chem. 1988, 27, 302–305.
1988JA7098 M. A. Bennett, G. B. Robertson, A. Rokicki, W. A. Wickramasinghe, J. Am. Chem. Soc. 1988, 110,
7098–7105.
1988JA8543 W. D. McGhee, T. Foo, F. J. Hollander, R. G. Bergman, J. Am. Chem. Soc. 1988, 110, 8543–8545.
1988JCS(P1)569 C. M. Lindsay, D. A. Widdowson, J. Chem. Soc., Perkin Trans. 1 1988, 569–573.
1988JGU26 N. I. Buvashkina, L. V. Kovalenko, L. I. Virin, I. Yu. Popova, J. Gen. Chem. USSR (Engl. Transl.)
1988, 58, 26–28.
1988JGU28 R. I. Yurchenko, E. É. Lavrova, A. G. Yurchenko, J. Gen. Chem. USSR (Engl. Transl.) 1988, 58,
28–30.
1988JGU1310 O. G. Sinyashin, I. Yu. Gorshunov, É. S. Batyeva, A. N. Pudovik, J. Gen. Chem. USSR (Engl.
Transl.) 1988, 58, 1310–1314.
1988JGU2384 A. S. Gordetsov, S. V. Zimina, V. K. Cherkasov, S. E. Skobeleva, V. L. Tsvetkova, T. I. Chulkova,
Yu. I. Dergunov, J. Gen. Chem. USSR (Engl. Transl.) 1988, 58, 2384–2387.
 Functions Containing a Carbonyl Group and Two Heteroatoms 483

1988JOM(339)111 P. Steil, U. Nagel, W. Beck, J. Organomet. Chem. 1988, 339, 111–124.

1988JOM(358)169 F. H. Elsner, T. D. Tilley, A. L. Rheingold, S. J. Geib, J. Organomet. Chem. 1988, 358, 169–183.
1988OM2234 Y.-W. Ge, P. R. Sharp, Organometallics 1988, 7, 2234–2236.
1988SC545 P. S. Reddy, P. Yadagiri, S. Lumin, D.-S. Shin, J. R. Falck, Synth. Commun. 1988, 18, 545–551.
1988TL3387 G. Märkle, S. Pfaum, Tetrahedron Lett. 1988, 29, 3387–3390.
1989AG(E)53 R. Appel, M. Poppe, Angew. Chem., Int. Ed. Engl. 1989, 28, 53–54.
1989CC900 W. J. Mills, L. J. Todd, J. C. Huffman, J. Chem. Soc., Chem. Commun. 1989, 900–902.
1989G301 L. Maresca, G. Natile, S. Pucci, B. Pelli, P. Traldi, Gazz. Chim. Ital. 1989, 119, 301–304.
1989IC4414 C. E. Philbin, A. E. Stiegman, S. C. Tenhaeff, D. R. Tyler, Inorg. Chem. 1989, 28, 4414–4417.
1989IS79 B. F. Spiegelvogel, F. U. Ahmed, A. T. McPhail, Inorg. Synth. 1989, 25, 79–85.
1989JA149 J. Arnold, T. D. Tilley, A. L. Rheingold, S. J. Geib, A. M. Arif, J. Am. Chem. Soc. 1989, 111,
149–164.
1989JA7424 P. Jernakoff, N. J. Cooper, J. Am. Chem. Soc. 1989, 111, 7424–7430.
1989JOM(368)103 G. Süss-Fink, M. Langenbahn, T. Jenke, J. Organomet. Chem. 1989, 368, 103–109.
1989JOM(371)303 W. P. Ehrenreich, M. Herberhold, A. F. Hill, J. Organomet. Chem. 1989, 371, 303–310.
1989JOM(379)311 G. Süss-Fink, T. Jenke, H. Heitz, M. A. Pellinghelli, A. Tiripicchio, J. Organomet. Chem. 1989, 379,
311–323.
1989OM324 D. M. Roddick, R. H. Heyn, T. D. Tilley, Organometallics 1989, 8, 324–330.
1989OM443 D. Seyferth, G. B. Womack, C. M. Archer, J. P. Fackler, Jr., D. O. Marler, Organometallics 1989,
8, 443–450.
1989OM2065 L. Huang, F. Ozawa, K. Osakada, A. Yamomoto, Organometallics 1989, 8, 2065–2068.
1990BCJ2736 T. Niitsu, N. Inamoto, K. Toyota, M. Yoshifuji, Bull. Chem. Soc. Jpn. 1990, 63, 2736–2738.
1990BCJ3658 M. K. Das, P. Mukherjee, S. Roy, Bull. Chem. Soc. Jpn. 1990, 63, 3658–3660.
1990CL1411 K. Narasaka, N. Saito, Y. Hayashi, H. Ichida, Chem. Lett. 1990, 1411–1414.
1990IC554 M. Mittakanti, K. W. Morse, Inorg. Chem. 1990, 29, 554–556.
1990IC3218 M. Mittakanti, M. R. M. D. Charandabi, K. W. Morse, Inorg. Chem. 1990, 29, 3218–3220.
1990JOC5017 P. J. Dunn, R. Häner, H. Rapoport, J. Org. Chem. 1990, 55, 5017–5025.
1990JOM(383)295 R. B. King, F.-J. Wu, E. M. Holt, J. Organomet. Chem. 1990, 383, 295–305.
1990JOM(383)587 L. Huang, F. Ozawa, K. Osakada, A. Yamomoto, J. Organomet. Chem. 1990, 383, 587–601.
1990JOM(387)C5 G. J. Irvine, C. E. F. Rickard, W. R. Roper, L. J. Wright, J. Organomet. Chem. 1990, 387, C5–C8.
1990OM1691 P. P. M. de Lange, H.-W. Frühauf, M. van Wijnkoop, K. Vrieze, Y. Wang, D. Heijdenrijk,
C. H. Stam, Organometallics 1990, 9, 1691–1694.
1990OM1958 H. Nakazawa, H. Nosaka, Y. Kushi, H. Yoneda, Organometallics 1990, 9, 1958–1963.
1990OM2603 L. Huang, F. Ozawa, A. Yamamoto, Organometallics 1990, 9, 2603–2611.
1990OM2612 L. Huang, F. Ozawa, A. Yamamoto, Organometallics 1990, 9, 2612–2620.
1990POL227 A. V. Seleznev, D. A. Bravo-Zhivotovskii, T. I. Vakul’skaya, M. G. Voronkov, Polyhedron 1990, 9,
227–231.
1990T7175 K. Afarinkia, C. W. Rees, J. I. G. Cadogan, Tetrahedron 1990, 46, 7175–7196.
1991BAU2099 B. A. Arbuzov, G. N. Nikonov, A. S. Balueva, R. M. Kamalov, M. A. Pudovik, R. R. Shagidullin,
A. Kh. Plymovatyi, R. Sh. Khadiullin, Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1991,
40, 2099–2102.
1991CB265 L. Weber, H. Schumann, Chem. Ber. 1991, 124, 265–269.
1991CB1795 R. Aumann, B. Trentmann, M. Dartmann, B. Krebs, Chem. Ber. 1991, 124, 1795–1803.
1991IC1046 W. J. Mills, C. H. Sutton, M. W. Baise, L. J. Todd, Inorg. Chem. 1991, 30, 1046–1052.
1991IC1955 C. J. Harlan, T. C. Wright, J. L. Atwood, S. G. Bott, Inorg. Chem. 1991, 30, 1955–1957.
1991IC2228 N. E. Miller, Inorg. Chem. 1991, 30, 2228–2231.
1991JA3800 C. A. Mirkin, K.-L. Lu, T. E. Snead, B. A. Young, G. L. Geoffroy, A. L. Rheingold, B. S. Haggerty,
J. Am. Chem. Soc. 1991, 113, 3800–3810.
1991JGU622 V. I. Kal’chenko, N. A. Parkhomenko, O. A. Aleksyuk, L. N. Markovskii, J. Gen. Chem. USSR
(Engl. Transl.) 1991, 61, 622–626.
1991JOM(403)293 S. S. Al-Juaid, Y. Derouiche, P. B. Hitchcock, P. D. Lickiss, A. G. Brook, J. Organomet. Chem.
1991, 403, 293–298.
1991JOM(413)379 H. Werner, B. Strecker, J. Organomet. Chem. 1991, 413, 379–397.
1991JOM(414)65 S. C. Srivastava, A. K. Shrimal, A. Srivastava, J. Organomet. Chem. 1991, 414, 65–69.
1991OM175 T.-M. Huang, J.-T. Chen, G.-H. Lee, Y. Wang, Organometallics 1991, 10, 175–179.
1991OM1305 G.-M. Yang, G.-H. Lee, S.-M. Peng, R.-S. Liu, Organometallics 1991, 10, 1305–1310.
1991OM2266 W. Tikkanen, J. W. Ziller, Organometallics 1991, 10, 2266–2273.
1991T6915 A. Sood, C. K. Sood, I. H. Hall, B. F. Spielvogel, Tetrahedron 1991, 47, 6915–6930.
1992BAU891 A. I. Yurtanov, Z. M. Adkhamova, S. K. Baidildaeva, Bull. Acad. Sci. USSR, Div. Chem. Sci.
(Engl. Transl.) 1992, 41, 891–894.
1992BAU1920 V. F. Rudchenko, S. M. Ignatov, R. G. Kostyanovskii, Bull. Acad. Sci. USSR, Div. Chem. Sci.
(Engl. Transl.) 1992, 41, 1920–1921.
1992EUP508191 R. Kaestner, N. Rieber, F. Merger, Eur. Pat. EP 508,191 (1992) (Chem. Abstr. 1993, 118, 22228).
1992HAC245 B. Singaram, Heteroatom Chem. 1992, 3, 245–249.
1992IC379 Y.-W. Ge, P. R. Sharp, Inorg. Chem. 1992, 31, 379–384.
1992IS211 F. Agbossou, E. J. O’Connor, C. M. Garner, N. Quirós Méndez, J. M. Fernández, A. T. Patton,
J. A. Ramsden, J. A. Gladysz, Inorg. Synth. 1992, 29, 211–225.
1992JA1256 C. A. Mirkin, T. J. Oyer, M. S. Wrighton, T. E. Snead, G. l. Geoffroy, J. Am. Chem. Soc. 1992,
114, 1256–1263.
1992JCR(S)34 H. Suzuki, C. Nakaya, Y. Matano, J. Chem. Res (S) 1992, 34–35.
1992JHC1189 E. Rivó, J. Reiter, J. Heterocycl. Chem. 1992, 29, 1189–1195.
1992JOC5020 A. O. Stewart, D. W. Brooks, J. Org. Chem. 1992, 57, 5020–5023.
484 Functions Containing a Carbonyl Group and Two Heteroatoms

1992JOC7339 R. Nomura, Y. Hasegawa, M. Ishimoto, T. Toyosaki, H. Matsuda, J. Org. Chem. 1992, 57,
7339–7342.
1992JOM(440)389 H. Werner, U. Brekau, O. Nürnberg, B. Zeier, J. Organomet. Chem. 1992, 440, 389–399.
1992JOM(441)155 M. J. Fernandez, J. Modredo, M. J. Rodriguez, M. C. Santamaria, L. A. Oro, J. Organomet. Chem.
1992, 441, 155–158.
1992JOU1635 M. V. Vovk, Yu. N. Davidyuk, A. N. Chernega, I. F. Tsymbal, L. I. Samarai, J. Org. Chem. USSR
(Engl. Transl.) 1992, 28, 1635–1643.
1992M607 K. A. Hackl, H. Falk, Monatsh. Chem. 1992, 123, 607–615.
1992OM3607 M. van Wijnkoop, P. P. M. de Lange, H.-W. Frühauf, K. Vrieze, Y. Wang, K. Goubitz, C. H. Stam,
Organometallics 1992, 11, 3607–3617.
1992T7629 S. E. Thomas, G. J. Tustin, A. Ibbotson, Tetrahedron 1992, 48, 7629–7640.
1992USP5155267 M. K. Faraj, U.S. Pat. 5,155,267 (1992) (Chem. Abstr. 1993, 118, 80639).
1993AG(E)896 J.-S. Tang, J. G. Verkade, Angew. Chem., Int. Ed. Engl. 1993, 32, 896–898.
1993CB1781 G. Schmid, H. Gehrke, H.-U. Kolorz, R. Boese, Chem. Ber. 1993, 126, 1781–1786.
1993CCC575 P. Kutschy, M. Dzurilla, V. Ficeri, D. Koščík, Collect. Czech. Chem. Commun. 1993, 58, 575–587.
1993EUP556841 E. Yamanaka, N. Tsuboniwa, T. Morimoto, M. Furukawa, S. Urano, Eur. Pat. EP 556,841 (1993)
(Chem. Abstr. 1994, 120, 106396).
1993GEP4127562 G. Stern, M. Muellner, M. Roessler, Ger. Pat. DE 4,127,562 (1993) (Chem. Abstr. 1993, 119, 27723).
1993H(35)1237 M. Avalos, R. Babiano, P. Cintas, J. L. Jiménez, J. C. Palacios, C. Valencia, Heterocycles 1993, 35,
1237–1246.
1993HAC455 T. Mizuno, M. Matsumoto, I. Nishiguchi, T. Hirashima, Heteroatom Chem. 1993, 4, 455–458.
1993IC3640 O. C. P. Beers, J. G. P. Delis, W. P. Mul, K. Vrieze, C. J. Elsevier, W. J. J. Smeets, A. L. Spek,
Inorg. Chem. 1993, 32, 3640–3647.
1993IJC(B)779 B. Kumar, H. Kumar, S. Arora, Indian J. Chem., Sect. B 1993, 32, 779–782.
1993JCA631 K.-T. Li, Y.-J. Peng, J. Catal. 1993, 143, 631–634.
1993JCS(D)1031 E. A. V. Ebsworth, N. Robertson, L. J. Yellowlees, J. Chem. Soc., Dalton Trans. 1993, 1031–1037.
1993JGU226 A. A. Prischenko, D. A. Pisarnitskii, M. V. Livantsov, V. S. Petrosyan, Russ. J. Gen. Chem. (Engl.
Transl.) 1993, 63, 226–228.
1993JGU1675 V. G. Sakhibullina, N. A. Polezhaeva, D. A. Bagautdinova, B. A. Arbuzov, Russ. J. Gen. Chem.
(Engl. Transl.) 1993, 63, 1675–1677.
1993JHC897 S. Massa, A. Mai, R. Di Santo, M. Artico, J. Heterocycl. Chem. 1993, 30, 897–903.
1993JOC1932 Y. Nambu, T. Endo, J. Org. Chem. 1993, 58, 1932–1934.
1993JOM(456)85 W. Petz, J. Organomet. Chem. 1993, 456, 85–88.
1993JOU1464 V. G. Shtamburg, A. A. Dmitrenko, A. P. Pleshkova, L. M. Pritykin, Russ. J. Org. Chem. (Engl.
Transl.) 1993, 29, 1464–1470.
1993MI64 P. Kutschy, M. Dzurilla, V. Ficeri, Chem. Pap. 1993, 47, 64–66. (Chem. Abstr. 1993, 119, 249889)
1993MI655 P. Jewess, J. P. Whiteleggee, P. Camilleri, J. R. Bowyer, J. Label. Compd. Radiopharm. 1993, 33,
655–669.
1993OM1725 P. Blandon, M. Dekker, G. R. Knox, D. Willison, G. A. Jaffari, R. J. Doedens, K. W. Muir,
Organometallics 1993, 12, 1725–1741.
1993OM3410 G. Poszmik, P. J. Carroll, B. B. Wayland, Organometallics 1993, 12, 3410–3417.
1993OPP600 K. Ramadas, N. Srinivasan, Org. Prep. Proc. Int. 1993, 25, 600–601.
1993PS(76)139 C. E. McKenna, A. Khare, J.-Y. Ju, Z.-M. Li, G. Duncan, Y.-C. Cheng, R. Kilkuskie, Phosphorus,
Sulfur Silicon Relat. Elem. 1993, 76, 139–142.
1993PS(85)161 V. I. Lachkova, G. Petrov, A. H. Hussein, Phosphorus, Sulfur, Silicon Relat. Elem. 1993, 85,
161–168.
1993S111 H. Wamhoff, W. Lamers, Synthesis 1993, 111–116.
1993SC1427 M. A. Abdel-Rahman, Synth. Commun. 1993, 23, 1427–1436.
1993SC2065 F. El Guemmont, A. Foucaud, Synth. Commun. 1993, 23, 2065–2070.
1993T2655 M. Avalos, R. Babiano, P. Cintas, J. L. Jiménez, J. C. Palacios, C. Valencia, Tetrahedron 1993, 49,
2655–2675.
1993T2676 M. Avalos, R. Babiano, P. Cintas, J. L. Jiménez, J. C. Palacios, C. Valencia, Tetrahedron 1993, 49,
2676–2690.
1993T4419 S. G. Davies, A. A. Mortlock, Tetrahedron 1993, 49, 4419–4438.
1993T9973 Q. Wang, A. Amer, S. Mohr, E. Ertel, J. C. Jochims, Tetrahedron 1993, 49, 9973–9986.
1993TL3857 Y. Fort, C. Gottardi, P. Caubère, Tetrahedron Lett. 1993, 34, 3857–3860.
1993TL7953 A. J. Fairbanks, R. P. Elliott, C. Smith, A. Hui, G. Way, R. Storer, H. Taylor, D. J. Watkins,
B. G. Winchester, G. W. J. Fleet, Tetrahedron Lett. 1993, 34, 7953–7956.
1993USP5198582 J. S. Oh, S. M. Lee, U.S. Pat. 5,198,582 (1993) (Chem. Abstr. 1993, 119, 180545).
1993USP5206362 G. P. Speranza, D. H. Champion, U.S. Pat. 5,206,362 (1993) (Chem. Abstr. 1993, 119, 160330).
1994AP469 A. Thom, G. Zinner, Arch. Pharm. (Weinheim, Ger.) 1994, 327, 469–475.
1994AP819 W. Löwe, N. Matzanke, T. Rütjes, Arch. Pharm. (Weinheim, Ger.) 1994, 327, 819–823.
1994BAU821 A. G. Korepin, P. V. Galkin, N. I. Golovina, R. F. Trofimova, V. V. Avdonin, E. P. Kirpichev,
Yu. I. Rubtsov, G. V. Lagodzinskaya, M. V. Loginova, Russ. Chem. Bull. (Engl. Transl.) 1994, 43,
821–825.
1994BAU1430 E. E. Korshin, L. I. Sabirova, Ya. A. Levin, Russ. Chem. Bull. (Engl. Transl.) 1994, 43, 1430.
1994CB711 W. Förtsch, F. Hampel, R. Schobert, Chem. Ber. 1994, 127, 711–715.
1994CC1249 P. G. Edwards, M. B. Hursthouse, K. M. A. Malik, J. S. Parry, J. Chem. Soc., Chem. Commun.
1994, 1249–1250.
1994CCC495 F. Gregáň, V. Kettmann, J. Csöllei, P. Novomeský, Collect. Czech. Chem. Commun. 1994, 59,
495–498.
1994CCC2663 M. Dzurilla, P. Kutschy, J. Imrich, S. Bartoš, Collect. Czech. Chem. Commun. 1994, 59, 2663–2676.
 Functions Containing a Carbonyl Group and Two Heteroatoms 485

1994CL293 Y. Kawano, K. Sugawara, H. Tobita, H. Ogino, Chem. Lett. 1994, 293–296.

1994CL2299 N. Yamamoto, M. Isobe, Chem. Lett. 1994, 2299–2302.
1994CPB2108 M. L. López-Rodríguez, M. J. Morcillo, F. Benito, B. Benhamu, E. Fernandez, M. Garrido,
L. Orensanz, Chem. Pharm. Bull. 1994, 42, 2108–2112.
1994EUP629612 R. Callens, G. Blondeel, M. Anteunis, F. Becu, Eur. Pat. EP 629,612 (1994) (Chem. Abstr. 1995,
123, 133647).
1994H(38)235 O. Tsuge, T. Hatta, R. Mizuguchi, Heterocycles 1994, 38, 235–241.
1994HCA1267 H. Sigmund, W. Pfeiderer, Helv. Chim. Acta 1994, 77, 1267–1280.
1994IC253 J. D. Gargulak, W. L. Gladfelter, Inorg. Chem. 1994, 33, 253–257.
1994JA1016 M. Sprecher, D. Kost, J. Am. Chem. Soc. 1994, 116, 1016–1026.
1994JHC77 B. Refouvelet, J.-F. Robert, J. Couquelet, P. Tronche, J. Heterocycl. Chem. 1994, 31, 77–80.
1994JHC329 M. T. Cocco, C. Congiu, A. Massioni, V. Onnis, J. Heterocycl. Chem. 1994, 31, 329–334.
1994JHC1235 P. de Miguel, N. Martín, M. F. Braña, J. Heterocycl. Chem. 1994, 31, 1235–1239.
1994JHC1569 H. Furrer, H.-W. Fehlhaber, R. Wagner, J. Heterocycl. Chem. 1994, 31, 1569–1575.
1994JHC1689 J. J. Li, T. J. Hagen, R. A. Chrusciel, M. B. Norton, S. Tsymbalov, E. A. Hallinan, D. B. Reitz, J.
Heterocycl. Chem. 1994, 31, 1689–1696.
1994JOC1583 M. L. López-Rodríguez, M. J. Morcillo, M. Garrido, B. Benhamú, V. Pérez, J. G. de la Campa, J.
Org. Chem. 1994, 59, 1583–1585.
1994JOC1937 P. Majer, R. S. Randad, J. Org. Chem. 1994, 59, 1937–1938.
1994JOC4931 J. Tang, T. Mohan, J. G. Verkade, J. Org. Chem. 1994, 59, 4931–4938.
1994JOC6413 O. Chavignon, J. C. Teulade, D. Roche, M. Madesclaire, Y. Blanche, A. Gueiffier, J. L. Chabard,
G. Dauphin, J. Org. Chem. 1994, 59, 6413–6418.
1994JOC6487 J. Gante, H. Neunhoeffer, A. Schmidt, J. Org. Chem. 1994, 59, 6487–6489.
1994JOC7144 T. Sakai, T. Kodama, T. Fujimoto, K. Ohta, I. Yamamoto, J. Org. Chem. 1994, 59, 7144–7147.
1994JOM(465)297 J. M. Boncella, L. A. Villanueva, J. Organomet. Chem. 1994, 465, 297–304.
1994JOM(470)249 P. Giannoccaro, J. Organomet. Chem. 1994, 470, 249–252.
1994JOM(474)23 A. Orita, K. Ohe, S. Murai, J. Organomet. Chem. 1994, 474, 23–25.
1994NKK146 Y. Taguchi, A. Oishi, T. Tsuchiya, I. Shibuya, Nippon Kagaki Kaishi (J. Chem. Soc. Jpn.) 1994,
146–149. (Chem. Abstr. 1994, 121, 9345)
1994OM1214 S. G. Feng, P. S. White, J. L. Templeton, Organometallics 1994, 13, 1214–1223.
1994OM1533 A. Orita, K. Ohe, S. Murai, Organometallics 1994, 13, 1533–1536.
1994OM1751 M. Rahim, K. J. Ahmed, Organometallics 1994, 13, 1751–1756.
1994OM2423 W. Trakarnpruk, A. M. Arif, R. D. Ernst, Organometallics 1994, 13, 2423–2429.
1994OM4695 D. Seyferth, D. P. Ruschke, W. M. Davis, Organometallics 1994, 13, 4695–4703.
1994OPP357 J. Petrov, J. Atanassova, V. Ognyanova, Org. Prep. Proced. Int. 1994, 26, 357–360.
1994POL2599 I. Lázár, J. Emri, B. Györi, Z. Kovács, Polyhedron 1994, 13, 2599–2604.
1994RRC397 A. A. Hassan, A.-F. E. Mourad, Rev. Roum. Chim. 1994, 39, 397–404.
1994S56 I. Jaafar, G. Francis, R. Danion-Bougot, D. Danion, Synthesis 1994, 56–60.
1994S782 M. S. Novikov, A. F. Khlebnikov, A. A. Stepanov, R. R. Kostikov, Synthesis 1994, 782–784.
1994SL919 Y. Ichikawa, C. Kobayashi, M. Isobe, Synlett 1994, 919–921.
1994TL33 Z. Shi, R. P. Thummel, Tetrahedron Lett. 1994, 35, 33–36.
1994TL2729 H. Affandi, A. V. Bayquen, R. W. Read, Tetrahedron Lett. 1994, 35, 2729–2732.
1994TL4055 S. M. Hutchins, K. T. Chapman, Tetrahedron Lett. 1994, 35, 4055–4058.
1994TL6017 Y.-Y. Ku, R. R. Patel, B. A. Roden, D. P. Sawick, Tetrahedron Lett. 1994, 35, 6017–6020.
1994TL8891 A. J. Fairbanks, A. Hui, B. M. Skead, P. M. de Q. Lilley, R. B. Lamont, R. Storer, J. Saunders,
D. J. Watkins, G. W. J. Fleet, Tetrahedron Lett. 1994, 35, 8891–8894.
1994WOP06825 M. C. Dubroeucq, C. Guyon, PCT Int. WO (World Intellectual Property Organization Pat.) 94
06,825 (1994) (Chem. Abstr. 1994, 121, 109672).
1994WOP14820 E. J. Pepe, C. L. Schilling Jr., E. W. Bennett, PCT Int. WO (World Property Organization Pat.) 94
14,820 (1994) (Chem. Abstr. 1994, 121, 205664).
1995AJC1651 M. I. Bruce, J. R. Hinchliffe, B. W. Skelton, A. H. White, Aust. J. Chem. 1995, 48, 1651–1657.
1995AP393 T. Höppner, H. G. Schweim, Arch. Pharm. (Weinheim, Ger.) 1995, 328, 393–395.
1995BSB411 M. Hedayatullah, A. Challier, A. Roger, I. Nachawati, Bull. Soc. Chim. Belg. 1995, 104, 411–414.
1995CL759 C. Raposo, M. Almaraz, M. Martín, V. Weinrich, M. L. Mussóns, V. Alcázar, Chem. Lett. 1995,
759–760.
1995COFGT(6)499 A. F. Hegarty, L. J. Drennan, Functions containing a carbonyl group and two heteroatoms other
than a halogen or chalcogen, in Comprehensive Organic Functional Group Transformations, A. R.
Katritzky, O. Meth-Cohn, C. W. Rees, Eds., Elsevier, Oxford, 1995, Vol. 6, pp. 499–526.
1995COMCII Comp. Organomet. Chem., 1st edn., Elsevier, Oxford, 1995.
1995EUP643049 A. Yanagi, Y. Watanabe, S. Narabu, Eur. Pat. EP 643,049 (1995) (Chem. Abstr. 1995, 122, 265384).
1995EUP646577 A. Yanagi, Y. Watanabe, S.-I. Narabu, Eur. Pat. EP 646,577 (1995) (Chem. Abstr. 1995, 123,
83371).
1995EUP670316 H. Naruse, H. Mizuta, S. Umeda, T. Nagata, Eur. Pat. EP 670,316 (1995) (Chem. Abstr. 1995, 123,
314035).
1995GEP4343595 J. Kluth, K.-H. Mueller, Ger. Pat. DE 4,343,595 (1995) (Chem. Abstr. 1995, 123, 286041).
1995GEP4405056 M. Wiesenfeldt, B. Siegel, M. Patsch, Ger. Pat. DE 4,405,056 (1995) (Chem. Abstr. 1995, 123,
339409).
1995JA4700 J.-O. Baeg, C. Bensimon, H. Alper, J. Am. Chem. Soc. 1995, 117, 4700–4701.
1995JAP(K)06239805 N. Takamatsu, N. Kuzuha, Jpn. Kokai JP 06,239,805 (1995) (Chem. Abstr. 1995, 122, 9488).
1995JAP(K)0761975 Y. Iwasawa, N. Tanaka, K. Akimoto, M. Nomura, K. Suzuki, Jpn. Kokai JP 07 61,975 (1995)
(Chem. Abstr. 1995, 123, 33090).
1995JCS(P1)377 Y. Ichikawa, C. Kobayashi, M. Isobe, J. Chem. Soc., Perkin Trans. 1 1995, 377–382.
486 Functions Containing a Carbonyl Group and Two Heteroatoms

1995JCS(P1)2783 Y. Wang, M. F. G. Stevens, W. T. Thomson, B. P. Shutts, J. Chem. Soc., Perkin Trans. 1 1995,
2783–2787.
1995JGU88 V. I. Manov-Yuvenskii, Russ. J. Gen. Chem. (Engl. Transl.) 1995, 65, 88–91.
1995JHC13 G. Heinisch, B. Matuszczak, G. Pürstinger, D. Rakowitz, J. Heterocycl. Chem. 1995, 32, 13–16.
1995JHC995 G. Verardo, A. G. Giumanini, F. Gorassini, P. Strazzolini, F. Benetollo, G. Bombieri, J. Hetero-
cycl. Chem. 1995, 32, 995–1001.
1995JHC1141 G. M. Coppola, R. E. Damon, J. Heterocycl. Chem. 1995, 32, 1141–1144.
1995JHC1625 D.-K. Kim, G. Kim, J. Lim, K. H. Kim, J. Heterocycl. Chem. 1995, 32, 1625–1629.
1995JOC321 F. D. Deroose, P. J. De Clercq, J. Org. Chem. 1995, 60, 321–330.
1995JOC6448 J. Scheerder, J. F. J. Engbersen, A. Casnati, R. Ungaro, D. N. Reinhoudt, J. Org. Chem. 1995, 60,
6448–6454.
1995LA415 H. J. Bestmann, W. Haas, K. Witzgall, A. Ricci, D. Lazzari, A. degl’Innocenti, G. Seconi,
P. Dembech, Liebigs Ann. Chem. 1995, 415–418.
1995OM131 M. Galakhov, A. Martín, M. Mena, F. Palacios, C. Yélamos, P. R. Raithby, Organometallics 1995,
14, 131–136.
1995OM1525 W. Tikkanen, A. L. Kim, K. B. Lam, K. Ruekert, Organometallics 1995, 14, 1525–1528.
1995OM4781 M. van Wijnkoop, P. P. M. de Lange, H.-W. Frühauf, K. Vrieze, W. J. J. Smeets, A. L. Spek,
Organometallics 1995, 14, 4781–4791.
1995PHA379 W. Hanefeld, J. Landwehr, Pharmazie 1995, 50, 379–382.
1995S1529 J. Barluenga, C. del Poso, B. Olano, Synthesis 1995, 1529–1533.
1995SC2467 C. F. Cooper, S. J. Falcone, Synth. Commun. 1995, 25, 2467–2474.
1995SL605 I. Candiani, W. Cabri, F. Zarini, A. Bedeschi, S. Penco, Synlett 1995, 605–606.
1995TL2021 I. V. Shevchenko, Tetrahedron Lett. 1995, 36, 2021–2024.
1995TL2665 R. Saladino, C. Crestini, R. Bernini, E. Mincione, R. Ciafrino, Tetrahedron Lett. 1995, 36,
2665–2668.
1995TL2741 Z. Shi, R. P. Thummel, Tetrahedron Lett. 1995, 36, 2741–2744.
1995TL6257 D.-K. Kim, Y.-W. Kim, J. Gam, J. Lim, K. H. Kim, Tetrahedron Lett. 1995, 36, 6257–6260.
1995WOP00509 C. Suzuki, K. Masuda, M. Tamaru, M. Inamori, N. Takefuji, K. Yanagisawa, Y. Ogawa, PCT Int.
(World Intellectual Property Organization Pat.) WO 95 00,509 (1995) (Chem. Abstr. 1995, 122,
265402).
1995ZAAC34 G. Becker, G. Heckmann, K. Hübler, W. Schwarz, Z. Anorg. Allg. Chem. 1995, 621, 34–46.
1996EUP692473 P. Vacca, M. Frezzati, Eur Pat. EP 692,473 (1996) (Chem. Abstr. 1996, 124, 260858).
1996EUP692476 S. Antons, H. Fiege, Eur. Pat. EP 692,476 (1996) (Chem. Abstr. 1996, 124, 261039).
1996JCS(D)4431 H. G. Raubenheimer, M. Desmet, P. Olivier, G. J. Kruger, J. Chem. Soc., Dalton Trans. 1996,
4431–4438.
1996JGU349 M. A. Pudovik, N. E. Krepysheva, R. Kh. Al’myanova, R. M. Kamalov, A. N. Pudovik, Russ. J.
Gen. Chem. (Engl. Transl.) 1996, 66, 349–352.
1996JGU1867 A. A. Prischenko, M. V. Livantsov, Zh. Yu. Goncharova, L. I. Livantsova, O. P. Novikova,
E. V. Grigor’ev, Russ. J. Gen. Chem. (Engl. Transl.) 1996, 66, 1867–1868.
1996JHC943 W. Löwe, N. Matzanke, J. Heterocycl. Chem. 1996, 33, 943–948.
1996JHC1259 J. M. Anglada, T. Campos, F. Camps, J. M. Moretó, L. I. Pagès, J. Heterocycl. Chem. 1996, 33,
1259–1270.
1996JHC1935 A. R. Katritzky, D. Cheng, P. Leeming, I. Ghiviriga, C. M. Hartshorn, P. J. Steel, J. Heterocycl.
Chem. 1996, 33, 1935–1941.
1996JMC1243 J. A. Picard, P. M. O’Brien, D. R. Sliskovic, M. K. Anderson, R. F. Bousley, K. L. Hamelehle,
B. R. Krause, R. L. Stanfield, J. Med. Chem. 1996, 39, 1243–1252.
1996JOC428 N. Kise, K. Kashiwagi, M. Watanabe, J.-i. Yoshida, J. Org. Chem. 1996, 61, 428–429.
1996JOC4175 M.-k. Leung, J.-L. Lai, K.-H. Lau, H.-h. Yu, H.-J. Hsiao, J. Org. Chem. 1996, 61, 4175–4179.
1996JOC8397 S. Buscemi, N. Vivona, T. Caronna, J. Org. Chem. 1996, 61, 8397–8401.
1996OM1134 M. D. Fryzuk, M. Mylvaganam, M. J. Zaworotko, L. R. MacGillivray, Organometallics 1996, 15,
1134–1138.
1996OM1251 M. Tamm, T. Lügger, F. E. Hahn, Organometallics 1996, 15, 1251–1256.
1996OM2148 N. Feiken, P. Schreuder, R. Sienbenlist, H.-W. Frühauf, K. Vrieze, H. Kooijman, N. Veldman,
A. L. Spek, J. Fraanje, K. Goubitz, Organometallics 1996, 15, 2148–2169.
1996OPP173 N. Choy, K. Y. Moon, C. Park, Y. C. Son, W. H. Jung, H.-i. Choi, C. S. Lee, C. R. Kim, S. C. Kim,
H. Yoon, Org. Prep. Proced. Int. 1996, 28, 173–177.
1996POL4355 J. B. Arterburn, Y. Wu, W. Quintana, Polyhedron 1996, 15, 4355–4359.
1996SC331 R. Freer, A. McKillop, Synth. Commun. 1996, 26, 331–349.
1996SC783 F. Plénat, M. Cassagne, H. J. Cristau, Synth. Commun. 1996, 26, 783–791.
1996SC2941 F. Plénat, M. Cassagne, H. J. Cristau, Synth. Commun. 1996, 26, 2941–2955.
1996SC3685 M. Hatam, J. R. Goerlich, R. Schmutzler, H. Gröger, J. Martens, Synth. Commun. 1996, 26,
3685–3698.
1996SC4253 T. Patonay, E. Patonay-Péli, L. Zolnai, F. Mogyoródi, Synth. Commun. 1996, 26, 4253–4265.
1996SL502 H.-J. Knölker, T. Braxmeier, G. Schlechtingen, Synlett 1996, 502–504.
1996SL507 M. Lamothe, M. Perez, V. Colovray-Gotteland, S. Halazy, Synlett 1996, 507–508.
1996T8581 I. López, A. Diez, M. Rubiralta, Tetrahedron 1996, 52, 8581–8600.
1996TL1217 E. Bon, R. Réau, G. Bertrand, D. C. H. Bigg, Tetrahedron Lett. 1996, 37, 1217–1220.
1996TL1945 C. Yuan, R. M. Williams, Tetrahedron Lett. 1996, 37, 1945–1948.
1996TL2361 A. G. Romero, W. H. Darlington, E. J. Jacobsen, J. W. Mickelson, Tetrahedron Lett. 1996, 37,
2361–2364.
1996TL4439 B. O. Buckman, R. Mohan, Tetrahedron Lett. 1996, 37, 4439–4442.
1996TL5835 S. Hanessian, R.-Y. Yang, Tetrahedron Lett. 1996, 37, 5835–5838.
 Functions Containing a Carbonyl Group and Two Heteroatoms 487

1996USP5508400 W. W. Wilkerson, J. D. Rodgers, U.S. Pat. 5,508,400 (1996) (Chem. Abstr. 1996, 125, 86693).
1997BOC277 K. W. Maurer, G. L. Kenyon, Bioorg. Chem. 1997, 25, 277–281.
1997BSF623 E. Marchand, G. Morel, Bull. Soc. Chim. Fr. 1997, 134, 623–634.
1997CC1799 Z. Berente, B. Gyori, J. Chem. Soc., Chem. Commun. 1997, 1799–1800.
1997CC2311 M. C. Elliott, E. Kruiswijk, J. Chem. Soc., Chem. Commun. 1997, 2311–2312.
1997HCA121 F. Glarner, S. R. Thornton, D. Schärer, G. Bernardinelli, U. Burger, Helv. Chim. Acta 1997, 80,
121–127.
1997HCA966 C. Jentgens, R. Hofmann, A. Guggisberg, S. Bienz, M. Hesse, Helv. Chim. Acta 1997, 80, 966–978.
1997IC4753 Y. Wu, P. J. Carroll, S. O. Kang, W. Quintana, Inorg. Chem. 1997, 36, 4753–4761.
1997JCS(P1)2319 C. A. Ramsden, H. L. Rose, J. Chem. Soc., Perkin Trans. 1 1997, 2319–2327.
1997JOC3230 M. M. Sim, A. Ganesan, J. Org. Chem. 1997, 62, 3230–3235.
1997JOC3858 C. J. Salomon, E. Breuer, J. Org. Chem. 1997, 62, 3858–3861.
1997JOC4155 A. R. Katritzky, D. P. M. Pleynet, B. Yang, J. Org. Chem. 1997, 62, 4155–4158.
1997JOC5380 E. P. Schreiner, A. Pruckner, J. Org. Chem. 1997, 62, 5380–5384.
1997JOM(541)423 S. Mihan, T. Weidmann, V. Weinrich, D. Fenske, W. Beck, J. Organomet. Chem. 1997, 541,
423–439.
1997OM2562 T. Kondo, S. Kotachi, Y. Tsuji, Y. Watanabe, T.-a. Mitsudo, Organometallics 1997, 16, 2562–2570.
1997OM5595 S. Anderson, D. J. Cook, A. F. Hill, Organometallics 1997, 16, 5595–5597.
1997S1189 B. Thavoneknam, Synthesis 1997, 1189–1194.
1997SC2357 K. Ramadas, N. Janarthanan, Synth. Commun. 1997, 27, 2357–2362.
1997SL1184 O. Braun, F. Vögtle, Synlett 1997, 1184–1186.
1997TL931 A. Nefzi, J. M. Ostresh, J.-P. Meyer, R. A. Houghten, Tetrahedron Lett. 1997, 38, 931–934.
1997TL2065 A. B. Dyatkin, Tetrahedron Lett. 1997, 38, 2065–2066.
1997TL4603 S. W. Kim, S. Y. Ahn, J. S. Koh, J. H. Lee, S. Ro, H. Y. Cho, Tetrahedron Lett. 1997, 38,
4603–4606.
1997TL5335 J. A. W. Kruijtzer, D. J. Lefeber, R. M. J. Liskamp, Tetrahedron Lett. 1997, 38, 5335–5338.
1997WOP47626 K. Hirai, T. Yano, N. Okano, K. Ikemoto, T. Yoshii, S. Ugai, T. Ueda, PCT Int. Appl. (World
Intellectual Property Organization Pat. Appl.) WO 97 47,626 (1997) (Chem. Abstr. 1998, 128,
61517).
1998ACS1141 M. Pan, T. Benneche, Acta Chem. Scand. 1998, 52, 1141–1143.
1998CC513 F. Bigi, R. Maggi, G. Sartori, E. Zambonin, J. Chem. Soc., Chem. Commun. 1998, 513–514.
1998CC2703 J. Yoon, C.-W. Cho, H. Han, K. D. Janda, J. Chem. Soc., Chem. Commun. 1998, 2703–2704.
1998EJO183 M. Wenzel, R. Beckert, W. Günther, H. Görls, Eur. J. Org. Chem. 1998, 183–187.
1998EJO379 K. Bast, M. Behrens, T. Durst, R. Grashey, R. Huisgen, R. Schiffer, R. Temme, Eur. J. Org. Chem.
1998, 379–385.
1998EUP846679 T. Hayashi, J. Yasuoka, Eur. Pat. EP 846,679 (1998) (Chem. Abstr. 1998, 129, 40921).
1998EUP879816 N. Sasaki, B. Sawano, M. Matsumoto, T. Kawabata, Eur. Pat. Appl. EP 879,816 (1998) (Chem.
Abstr. 1998, 129, 343335).
1998JCR(S)442 M. Xian, J. Lu, X. Zhu, L. Mu, J.-P. Cheng, J. Chem. Res. (S) 1998, 442–443.
1998JCS(P1)2377 R. Varma, S. K. Ghosh, J. Chem. Soc., Perkin Trans. 1 1998, 2377–2381.
1998JCS(P1)3127 J. Habermann, S. V. Ley, J. S. Scott, J. Chem. Soc., Perkin Trans. 1 1998, 3127–3130.
1998JHC261 F. Chau, J.-C. Malanda, R. Milcent, J. Heterocycl. Chem. 1998, 35, 261–263.
1998JOC2424 J. P. Collman, Z. Wang, A. Straumanis, J. Org. Chem. 1998, 63, 2424–2425.
1998JOC4802 M. A. Scialdone, S. W. Shuey, P. Soper, Y. Hamuro, D. M. Burns, J. Org. Chem. 1998, 63,
4802–4807.
1998JOC8515 P. Y. Chong, S. Z. Janicki, P. A. Petillo, J. Org. Chem. 1998, 63, 8515–8521.
1998JOC9252 A. Dondoni, D. Perrone, M. Rinaldi, J. Org. Chem. 1998, 63, 9252–9264.
1998JOM(563)1 A. L. Jorgenson, R. A. Nadeau, V. G. Young, Jr., W. L. Gladfelter, J. Organomet. Chem. 1998,
563, 1–6.
1998JOM(568)241 W. Malisch, A. Spörl, H. Pfister, J. Organomet. Chem. 1998, 568, 241–245.
1998JOM(568)247 W. Malisch, K. Thirase, J. Reising, J. Organomet. Chem. 1998, 568, 247–252.
1998MI129 S. W. Kim, J. S. Koh, E. J. Lee, S. Ro, Mol. Diversity 1998, 3, 129–132.
1998MI139 A. M. Yu, H. Z. Yang, Z. P. Zhang, Chin. Chem. Lett. 1998, 9, 139–142.
1998OM131 T.-F. Wang, C.-C. Hwu, C.-W. Tsai, Y.-S. Wen, Organometallics 1998, 17, 131–138.
1998OM2945 Y. Tang, J. Sun, J. Chen, Organometallics 1998, 17, 2945–2952.
1998PHA607 N. Mishriky, F. M. Asaad, Y. A. Ibrahim, A. S. Girgis, Pharmazie 1998, 53, 607–611.
1998S967 M. A. A. Meziane, M. Rahmouni, J. P. Bazureau, J. Hamelin, Synthesis 1998, 967–969.
1998SC1415 M. Pan, T. Benneche, Synth. Commun. 1998, 28, 1415–1419.
1998SC3665 R. A. Mekheimer, Synth. Commun. 1998, 28, 3665–3674.
1998SL1325 C. G. Ferguson, G. R. J. Thatcher, Synlett 1998, 1325–1326.
1998T10789 F. Fabis, S. Jolivet-Fouchet, M. Robba, H. Landelle, S. Rault, Tetrahedron 1998, 54, 10789–10800.
1998TL179 G. P. Wei, G. B. Philips, Tetrahedron Lett. 1998, 39, 179–182.
1998TL1121 S. S. Nikam, B. E. Kornberg, S. E. Ault-Justus, M. F. Rafferty, Tetrahedron Lett. 1998, 39,
1121–1124.
1998TL3609 M. Anbazhagan, A. R. A. S. Deshmukh, S. Rajappa, Tetrahedron Lett. 1998, 39, 3609–3612.
1998TL3631 B. A. Dressman, U. Singh, S. W. Kaldor, Tetrahedron Lett. 1998, 39, 3631–3634.
1998TL6267 R. A. Batey, V. Santhakumar, C. Yoshina-Ishii, S. D. Taylor, Tetrahedron Lett. 1998, 39,
6267–6270.
1998TL7811 J. W. Nieuwenhuijzen, P. G. M. Conti, H. C. J. Ottenheijm, J. T. M. Linders, Tetrahedron Lett.
1998, 39, 7811–7814.
1998USP5817814 M. J. Konz, H. R. Wendt, U.S. Pat. 5,817,814 (1998) (Chem. Abstr. 1998, 129, 290143).
1999H(50)67 M. Komatsu, S. Tamabuchi, S. Minakata, Y. Ohshiro, Heterocycles 1999, 50, 67–70.
488 Functions Containing a Carbonyl Group and Two Heteroatoms

1999H(51)2035 M. Takahashi, Y. Kadowaki, Y. Uno, Y. Nakano, Heterocycles 1999, 51, 2035–2039.

1999HCO473 H. Abdel Hamid, A. Moussad, E. S. Ramadan, E. S. H. El Ashry, Heterocycl. Commun. 1999, 5,
473–480.
1999IC3494 A. L. Balch, M. M. Olmstead, J. C. Vickery, Inorg. Chem. 1999, 38, 3494–3499.
1999JCO361 C.-M. Sun, J.-Y. Shey, J. Comb. Chem. 1999, 1, 361–363.
1999JCR(S)710 M. M. Mojtahedi, M. R. Saidi, M. Bolourtchian, J. Chem. Res. (S) 1999, 710–711.
1999JCS(P1)677 K. M. Madyastha, G. R. Sridhar, J. Chem. Soc., Perkin Trans. 1 1999, 677–680.
1999JHC1327 W.-D. Pfeiffer, A. Hetzheim, P. Pazdera, A. Bodtke, J. Mücke, J. Heterocycl. Chem. 1999, 36,
1327–1336.
1999JOC1004 F. Bigi, B. Frullanti, R. Maggi, G. Sartori, E. Zambonin, J. Org. Chem. 1999, 64, 1004–1006.
1999JOC2835 B. Linclau, A. K. Sing, D. P. Curran, J. Org. Chem. 1999, 64, 2835–2842.
1999JOM(577)167 A. Ceccon, P. Ganis, M. Imhoff, F. Manoli, S. Santi, A. Venzo, J. Organomet. Chem. 1999, 577,
167–173.
1999JOM(580)117 C. Roveda, E. Cariati, E. Lucenti, D. Roberto, J. Organomet. Chem. 1999, 580, 117–127.
1999OL961 J. E. McCusker, C. A. Grasso, A. D. Main, L. McElwee-White, Org. Lett. 1999, 1, 961–964.
1999OM187 P. Nombel, N. Lugan, B. Donnadieu, G. Lavigne, Organometallics 1999, 18, 187–196.
1999OM748 R. J. Madhushaw, S. R. Cheruki, K. Narkunan, G.-H. Lee, S.-M. Peng, R.-S. Liu, Organometallics
1999, 18, 748–752.
1999OM1353 R. Khayatpoor, J. R. Shapley, Organometallics 1999, 18, 1353–1356.
1999OM2459 Y. Tang, J. Sun, J. Chen, Organometallics 1999, 18, 2459–2465.
1999OM4700 S. R. Foley, G. P. A. Yap, D. S. Richeson, Organometallics 1999, 18, 4700–4705.
1999PS(144)313 C. E. McKenna, B. A. Kashemirov, Z.-M. Li, Phosphorus, Sulfur Silicon Relat. Elem. 1999, 144,
313–316.
1999S453 P. G. Baraldi, B. Cacciari, R. Romagnoli, G. Spalluto, Synthesis 1999, 453–458.
1999S943 M. E. F. Braibante, H. S. Braibante, E. R. Costenaro, Synthesis 1999, 943–946.
1999S1907 J. L. Jiménez Blanco, C. Saitz Barría, J. M. Benito, C. Ortiz Mellet, J. Fuentes, F. Santoyo-
González, J. M. García Fernández, Synthesis 1999, 1907–1914.
1999SL1379 M. C. Elliott, A. E. Monk, E. Kruiswijk, D. E. Hibbs, R. L. Jenkins, D. V. Jones, Synlett 1999,
1379–1382.
1999T475 N. Coşkun, Tetrahedron 1999, 55, 475–484.
1999TL2749 D. Limal, V. Semetey, P. Dalbon, M. Jolivet, J.-P. Briand, Tetrahedron Lett. 1999, 40, 2749–2752.
1999TL2895 F. J. Weiberth, Tetrahedron Lett. 1999, 40, 2895–2898.
1999TL3235 S. Braverman, M. Cherkinsky, L. Kedrova, A. Reiselman, Tetrahedron Lett. 1999, 40, 3235–3238.
1999TL4501 P. Y. Chong, P. A. Petillo, Tetrahedron Lett. 1999, 40, 4501–4504.
1999TL5841 K.-H. Park, M. J. Kurth, Tetrahedron Lett. 1999, 40, 5841–5844.
1999TL6121 J. A. Patterson, R. Ramage, Tetrahedron Lett. 1999, 40, 6121–6124.
1999TL6545 B. E. Blass, M. Drowns, C. L. Harris, S. Liu, D. Potlock, Tetrahedron Lett. 1999, 40, 6545–6547.
1999TL8563 S. Curtet, M. Langlois, Tetrahedron Lett. 1999, 40, 8563–8566.
1999ZAAC1979 V. Plack, J. R. Goerlich, A. Fischer, R. Schmutzler, Z. Anorg. Allg. Chem. 1999, 625, 1979–1984.
1999ZN(B)385 R. Urban, K. Polborn, W. Beck, Z. Naturforsch., Teil B 1999, 54, 385–388.
2000BAU1202 A. V. Popov, A. N. Pushin, E. L. Luzina, Russ. Chem. Bull. (Engl. Transl.) 2000, 49, 1202–1206.
2000CAR161 V. M. Diaz Pérez, C. Ortiz Mellet, J. Fuentes, J. M. García Fernández, Carbohydr. Res. 2000, 326,
161–175.
2000CCA569 I. Butula, M. Jadrijević-Mladar Takač, Croat. Chem. Acta 2000, 73, 569–574.
2000CHE837 V. Mickevicius, A. Patupaite, Chem. Heterocycl. Compd. (Engl. Transl.) 2000, 36, 837–840.
2000EJI159 D. Carmona, J. Ferrer, J. M. Arilla, J. Reyes, F. J. Lahoz, S. Elipe, J. Modrego, L. A. Oro, Eur. J.
Inorg. Chem. 2000, 159–163.
2000EJM879 S. N. Pandeya, P. Yogeeswari, J. P. Stables, Eur. J. Med. Chem. 2000, 35, 879–886.
2000EJO2105 H. Tietz, O. Rademacher, G. Zahn, Eur. J. Org. Chem. 2000, 2105–2112.
2000GEP19830556 A. Stamm, J. Henkelmann, Ger. Pat. DE 19,830,556 (2000) (Chem. Abstr. 2000, 132, 64259).
2000HAC470 R. Chen, A. Schlossman, E. Breuer, G. Hägele, C. Tillman, J. M. Van Gelder, G. Golomb,
Heteroatom Chem. 2000, 11, 470–479.
2000HCO55 D. Geffken, S. Zilz, Heterocycl. Commun. 2000, 8, 55–58.
2000JA2966 K. C. Nicolaou, A. J. Roecker, J. A. Pfefferkorn, G.-Q. Cao, J. Am. Chem. Soc. 2000, 122,
2966–2967.
2000JCO710 S. Bräse, S. Dahmen, M. Pfefferkorn, J. Comb. Chem. 2000, 2, 710–715.
2000JCR(S)145 M. S. Khajavi, M. G. Dakamin, H. Hazarkhani, J. Chem. Res. (S) 2000, 145–147.
2000JCS(P1)2677 R. Johannesen, T. Benneche, J. Chem. Soc., Perkin Trans. 1 2000, 2677–2679.
2000JHC1247 M. El Haddad, M. Soukri, S. Lazar, A. Bennamara, G. Guillaumet, M. Akssira, J. Heterocycl.
Chem. 2000, 37, 1247–1252.
2000JMOC(A)11 J. E. McCusker, F. Qian, L. McElwee-White, J. Mol. Catal. A: Chem. 2000, 159, 11–17.
2000JOC1549 Y. Matsumura, Y. Satoh, O. Onomura, T. Maki, J. Org. Chem. 2000, 65, 1549–1551.
2000JOC3239 S. Gastaldi, S. M. Weinreb, D. Stien, J. Org. Chem. 2000, 65, 3239–3240.
2000JOC5216 J. E. McCusker, A. D. Main, K. S. Johnson, C. A. Grasso, L. McElwee-White, J. Org. Chem. 2000,
65, 5216–5222.
2000JOC5887 D. C. D. Butler, G. A. Inman, H. Alper, J. Org. Chem. 2000, 65, 5887–5890.
2000JOC6368 Y. Basel, A. Hassner, J. Org. Chem. 2000, 65, 6368–6380.
2000JOM(598)403 W. Petz, F. Weller, E. V. Avtonomov, J. Organomet. Chem. 2000, 598, 403–408.
2000JOM(607)156 R. S. Dickson, G. D. Fallon, W. R. Jackson, A. Polas, J. Organomet. Chem. 2000, 607, 156–163.
2000M463 K. Burger, J. Spengler, L. Hennig, R. Herzschuh, S. A. Essawy, Monatsh. Chem. 2000, 131,
463–473.
2000M953 S. Liu, X. Qian, J. Chen, G. Song, Monatsh. Chem. 2000, 131, 953–957.
 Functions Containing a Carbonyl Group and Two Heteroatoms 489

2000MI24 M. S. Khajavi, M. G. Dakamin, H. Hazarkhani, M. Hajihadi, F. Nikpour, Iran. J. Chem. Chem.

Eng. 2000, 19, 24–28.
2000MI55 B. Wan, S. Liao, D. Yu, Reactive Funct. Polym. 2000, 45, 55–59.
2000MI275 M. I. Bruce, M. G. Humphrey, Organomet. Chem. 2000, 28, 275–366.
2000MI285 R. T. Fell, B. Meunier, C. R. Acad. Sci. Paris, Serie IIc, Chem. 2000, 3, 285–288.
2000MI355 Y. Yang, S. Lu, Cuihua Xuebao 2000, 21, 355–358. (Chem. Abstr. 2000, 133, 334853)
2000MI405 M. S. Chorgade, K. Sadalapure, S. Adhikari, S. V. S. Lalitha, A. M. S. Murugaiah, P. R. Krishna,
B. S. Reddy, M. K. Gurjar, Carbohydr. Lett. 2000, 3, 405–410.
2000MI1152 Y. J. Ki, S. O. Kang, E. J. Cho, S. Jeon, K. C. Nam, Bull. Korean Chem. Soc. 2000, 21, 1152–1154.
2000OL2113 P. Y. Chong, P. A. Petillo, Org. Lett. 2000, 2, 2113–2116.
2000OL3309 M. T. Migawa, E. E. Swayze, Org. Lett. 2000, 2, 3309–3311.
2000OM15 S. Anderson, A. F. Hill, Y. T. Ng, Organometallics 2000, 19, 15–21.
2000OM72 Y. Tang, J. Sun, J. Chen, Organometallics 2000, 19, 72–80.
2000OM1661 W. D. Jones, K. A. Reynolds, C. K. Sperry, R. J. Lachicotte, S. A. Godleski, R. R. Valente,
Organometallics 2000, 19, 1661–1669.
2000OM2445 U. Segerer, J. Sieler, E. Hey-Hawkins, Organometallics 2000, 19, 2445–2449.
2000OM3754 M. K. Kolel-Veetil, M. A. Khan, K. M. Nicholas, Organometallics 2000, 19, 3754–3756.
2000OM3879 M. Aresta, P. Giannoccaro, I. Tommazi, A. Dibenedetto, A. M. Manotti Lanfredi, F. Ugozzoli,
Organometallics 2000, 19, 3879–3889.
2000MI115723 E. Georgescu, R. Vulturescu, Rom. Pat. RO 115,723 (2000) (Chem. Abstr. 2001, 134, 353174).
2000PHA490 J. R. Dimmock, S. C. Vashishta, J. P. Stables, Pharmazie 2000, 55, 490–494.
2000PS(158)67 K. Petrova, V. Kalcheva, A. Antonova, Phosphorus, Sulfur Silicon Relat. Elem. 2000, 158, 67–80.
2000PS(160)51 Z.-G. Li, Q.-M. Wang, R.-Q. Huang, J.-R. Cheng, J.-A. Ma, Phosphorus, Sulfur Silicon Relat.
Elem. 2000, 160, 51–59.
2000PS(160)141 A. M. Sh. El-Sharief, A. A. Atalla, A. M. Hussein, M. S. A. El-Gaby, A. A. Hassan, Phosphorus,
Sulfur Silicon Relat. Elem. 2000, 160, 141–158.
2000PS(164)161 M. J. Gil, A. Reliquet, F. Reliquet, J. C. Meslin, Phosphorus, Sulfur Silicon Relat. Elem. 2000, 164,
161–172.
2000S1229 F. Effenberger, J. M. Endtner, B. Miehlich, J. S. R. Münter, M. S. Vollmer, Synthesis 2000,
1229–1236.
2000SC1675 T. Mizuno, T. Kino, T. Ito, T. Miyata, Synth. Commun. 2000, 30, 1675–1688.
2000SC1937 J. Kitteringham, M. R. Shipton, M. Voyle, Synth. Commun. 2000, 30, 1937–1943.
2000SC2635 Z. Li, X. Wang, Y. Da, J. Chen, Synth. Commun. 2000, 30, 2635–2645.
2000SC3081 T. Mizuno, T. Kino, T. Ito, T. Miyata, Synth. Commun. 2000, 30, 3081–3089.
2000SC3405 X. Wang, Z. Li, Y. Da, J. Chen, Synth. Commun. 2000, 30, 3405–3411.
2000SC4543 X. Wang, Z. Li, Y. Da, Synth. Commun. 2000, 30, 4543–4553.
2000SL45 S. Wendeborn, Synlett 2000, 45–48.
2000SL1253 Y. Ichikawa, T. Nishiyama, M. Isobe, Synlett 2000, 1253–1256.
2000SL1779 A. P. Molchanov, D. I. Sipkin, Yu. B. Koptelov, R. R. Kostikov, Synlett 2000, 1779–1780.
2000T3697 T. Ullrich, P. Sulek, D. Binder, M. Pyerin, Tetrahedron 2000, 56, 3697–3701.
2000TL1159 S. Wu, J. M. Janusz, J. B. Sheffer, Tetrahedron Lett. 2000, 41, 1159–1163.
2000TL1165 S. Wu, J. M. Janusz, Tetrahedron Lett. 2000, 41, 1165–1169.
2000TL1487 A. Wahhab, J. Leban, Tetrahedron Lett. 2000, 41, 1487–1490.
2000TL1553 G. Guichard, V. Semetey, M. Rodríguez, J.-P. Briand, Tetrahedron Lett. 2000, 41, 1553–1557.
2000TL3983 M. Liley, T. Johnson, Tetrahedron Lett. 2000, 41, 3983–3985.
2000TL4307 S. P. Keen, S. M. Weinreb, Tetrahedron Lett. 2000, 41, 4307–4310.
2000TL5265 J. Azizian, M. Mehrdad, K. Jadidi, Y. Sarrati, Tetrahedron Lett. 2000, 41, 5265–5268.
2000TL6347 I. Vauthey, F. Valot, C. Gozzi, F. Fache, M. Lemaire, Tetrahedron Lett. 2000, 41, 6347–6350.
2000TL6387 S. Wendeborn, T. Winkler, I. Foisy, Tetrahedron Lett. 2000, 41, 6387–6391.
2000TL7065 C. Songkram, A. Tanatani, R. Yamasaki, K. Yamaguchi, H. Kagechika, Y. Endo, Tetrahedron
Lett. 2000, 41, 7065–7070.
2000TL7409 K.-H. Park, M. J. Kurth, Tetrahedron Lett. 2000, 41, 7409–7413.
2000TL10141 I. I. Gerus, N. V. Lyutenko, A. D. Kacharov, V. P. Kukhar, Tetrahedron Lett. 2000, 41,
10141–10145.
2000USP6127575 H. S. Kim, Y. l. Kim, H. J. Lee, M. J. Chung, S. D. Sang, U.S. Pat. 6,127,575 (2000) (Chem. Abstr.
2000, 133, 266307).
2000WOP002889 C. E. McKenna, B. A. Kashemirov, PCT Int. Appl. (World Intellectual Property Organization Pat.
Appl.) WO 00 002,889 (2000) (Chem. Abstr. 2000, 132, 78693).
2001BMCL271 K.-T. Huang, C.-M. Sun, Bioorg. Med. Chem. Lett. 2001, 11, 271–273.
2001CPB391 A. Z. M. S. Chowdhury, Y. Shibata, Chem. Pharm. Bull. 2001, 49, 391–395.
2001EJO1695 R. Ketcham, E. Schaumann, G. Adiwidjaja, Eur. J. Org. Chem. 2001, 1695–1699.
2001EJO1943 B. König, M. Pelka, M. Subat, I. Dix, P. G. Jones, Eur. J. Org. Chem. 2001, 1943–1949.
2001HAC68 Q. Wang, Z. Li, R. Huang, J. Cheng, Heteroatom Chem. 2001, 12, 68–72.
2001HCO233 J. E. Charris, J. N. Domínguez, S. E. López, Heterocycl. Commun. 2001, 7, 233–236.
2001IC2979 K. Herbst, M. Monari, M. Brorson, Inorg. Chem. 2001, 40, 2979–2985.
2001JAP(K)302640 N. Hirano, M. Saijo, Jpn. Kokai JP 2001 302, 640 (2001) (Chem. Abstr. 2001, 135, 331427).
2001JCA91 Y. Fu, T. Baba, Y. Ono, J. Catal. 2001, 197, 91–97.
2001JCO68 A. Nefzi, M. A. Giulianotti, R. A. Houghten, J. Comb. Chem. 2001, 3, 68–70.
2001JCO171 K.-H. Park, J. Ehrler, H. Spoerri, M. J. Kurth, J. Comb. Chem. 2001, 3, 171–176.
2001JCO189 A. N. Acharya, A. Nefzi, J. M. Ostresh, R. A. Houghten, J. Comb. Chem. 2001, 3, 189–195.
2001JCO278 A. Gopalsamy, H. Yang, J. Comb. Chem. 2001, 3, 278–283.
2001JCO354 A. Paio, R. F. Crespo, P. Seneci, M. Ciraco, J. Comb. Chem. 2001, 3, 354–359.
490 Functions Containing a Carbonyl Group and Two Heteroatoms

2001JCR(S)470 Z.-G. Li, R.-Q. Huang, J. Chem. Res. (S) 2001, 470–471.
2001JCS(D)3219 C. Jones, P. C. Junk, J. W. Steed, R. C. Thomas, T. C. Williams, J. Chem. Soc., Dalton Trans. 2001,
3219–3226.
2001JCS(P1)1241 B. L. Booth, I. M. Cabral, A. M. Dias, A. P. Freitas, A. M. Matos Beja, M. F. Proença,
M. R. Silva, J. Chem. Soc., Perkin Trans. 1 2001, 1241–1251.
2001JCS(P1)2012 J.-P. Meigh, M. Álvarez, J. A. Joule, J. Chem. Soc., Perkin Trans. 1 2001, 2012–2021.
2001JCS(P2)1247 J. Taillades, L. Boiteau, I. Beuzelin, O. Lagrille, J.-P. Biron, W. Vayaboury, O. Vandenabeele-
Trambouze, O. Giani, A. Commeyras, J. Chem. Soc., Perkin Trans. 2 2001, 1247–1254.
2001JGU1953 E. V. Ratsino, S. I. Radchenko, Russ. J. Gen. Chem. (Engl. Transl.) 2001, 71, 1953–1954.
2001JHC451 M. Pores-Makkay, G. Simig, J. Heterocycl. Chem. 2001, 38, 451–455.
2001JHC1097 S.-i. Nagai, S. Takemoto, T. Ueda, K. Mizatani, Y. Uozumi, H. Tokuda, J. Heterocycl. Chem.
2001, 38, 1097–1101.
2001JMC1475 S. V. Andurkar, C. Béguin, J. P. Stables, H. Kohn, J. Med. Chem. 2001, 44, 1475–1478.
2001JMC2344 C. Fotsch, J. D. Sonnenberg, N. Chen, C. Hale, W. Karbon, M. H. Norman, J. Med. Chem. 2001,
44, 2344–2356.
2001JOC2858 A. R. Katritzky, Z. Luo, Y. Fang, P. J. Steel, J. Org. Chem. 2001, 66, 2858–2861.
2001JOC4200 Y. Ichikawa, T. Nishiyama, M. Isobe, J. Org. Chem. 2001, 66, 4200–4205.
2001JOM(626)227 F. Montilla, E. Clara, T. Avilés, T. Casimiro, A. A. Ricardo, M. N. da Ponte, J. Organomet. Chem.
2001, 626, 227–232.
2001JOM(634)47 O. Blacque, H. Brunner, M. M. Kubicki, J.-C. Leblanc, W. Meier, C. Moise, Y. Mugnier,
A. Sadorge, J. Wachter, M. Zabel, J. Organomet. Chem. 2001, 634, 47–54.
2001JOU1611 I. V. Koval, T. G. Oleinik, Russ. J. Org. Chem. (Engl. Transl.) 2001, 37, 1611–1613.
2001JOU1747 M. V. Vovk, N. V. Mel’nichenko, V. A. Chornous, M. K. Bratenko, Russ. J. Org. Chem. (Engl.
Transl.) 2001, 37, 1747–1752.
2001MC32 K. Yu. Chegaev, A. M. Kravchenko, O. V. Lebedev, Yu. A. Strelenko, Mendeleev Commun. 2001,
32–33.
2001MI42 L. Pieters, J. Košmrlj, R. Lenaršič, M. Kočevar, S. Polanc, ARKIVOC 2001, 2, 42–50.
2001MI127 G. G. Shiue, R. Schirrmacher, C.-Y. Shiue, A. A. Alavi, J. Label. Cpd. Radiopharm. 2001, 44,
127–139.
2001MI133 E. Fidesser, N. Haider, R. Jbara, ARKIVOC 2001, 2, 133–139.
2001MI180 H. H. Fahmy, G. A. Soliman, Arch. Pharm. Res. 2001, 24, 180–189.
2001MI191 O. N. Leonov, V. M. Shcherbakov, V. M. Devichensky, L. Yu. Kryukova, E. A. Vorontsov,
S. L. Kuznetsov, L. N. Kryukov, Russ. J. Bioorg. Chem. (Engl. Transl.) 2001, 27, 191–194.
2001MI351 S. Samanta, A. Pain, S. Dutta, U. Sanyal, Acta Pol. Pharm. 2001, 58, 351–358.
2001MI404 K. M. Youssef, E. Al-Abdullah, H. El-Khamees, Med. Chem. Res. 2001, 10, 404–408.
2001MI799 H.-z. Yang, Y.-q. Deng, Huaxue Xuebao 2001, 59, 799–802. (Chem. Abstr. 2001, 135, 152610).
2001MI1135 C.-Y. Chiu, C.-N. Kuo, W.-F. Kuo, M.-Y. Yeh, J. Chin. Chem. Soc. 2001, 48, 1135–1142.
2001OL2313 N. A. Dales, R. S. Bohacek, K. A. Satyshur, D. H. Rich, Org. Lett. 2001, 3, 2313–2316.
2001OM3390 F. Ragaini, S. Cenini, E. Borsani, M. Dompé, E. Gallo, Organometallics 2001, 20, 3390–3398.
2001PHA361 A. M. Bruno, S. E. Asis, C. H. Gaozza, Pharmazie 2001, 56, 361–365.
2001SC1433 Z. Li, X. Wang, Y. Da, J. Chen, Synth. Commun. 2001, 31, 1433–1440.
2001SL222 M. Belley, J. Scheigetz, P. Dubé, S. Dolman, Synlett 2001, 222–225.
2001SL682 J. Röhrling, A. Potthast, T. Rosenau, T. Lange, A. Borgards, H. Sixta, P. Kosma, Synlett 2001,
682–684.
2001SL697 C. W. Phoon, M. M. Sim, Synlett 2001, 697–699.
2001SL914 G. A. Inman, D. C. D. Butler, H. Alper, Synlett 2001, 914–919.
2001TL1423 R. F. Cunico, Tetrahedron Lett. 2001, 42, 1423–1425.
2001TL1445 Q. Liu, N. W. Luedtke, Y. Tor, Tetrahedron Lett. 2001, 42, 1445–1447.
2001TL1973 W. Huang, S. Cheng, W. Sun, Tetrahedron Lett. 2001, 42, 1973–1974.
2001TL2161 F. Shi, Y. Deng, T. SiMa, H. Yang, Tetrahedron Lett. 2001, 42, 2161–2163.
2001TL5913 C. Songkram, R. Yamasaki, A. Tanatani, K. Takaishi, K. Yamaguchi, H. Kagechika, Y. Endo,
Tetrahedron Lett. 2001, 42, 5913–5916.
2001TL9131 J. Kraïem, L. Grosvalet, M. Perrin, B. B. Hassine, Tetrahedron Lett. 2001, 42, 9131–9133.
2001WOP04085 J. J. P. M. Goorden, J. J. De Wit, PCT Int. (World Intellectual Property Pat.) WO 01 04,085 (2001)
(Chem. Abstr. 2001, 134, 100571).
2001WOP05354 J. M. F. Lara Ochoa, J. A. de la Torre Garcia, F. Franco Andrade, PCT Int. Appl. (World
Intellectual Property Pat. Appl.) WO 01 05,354 (2001) (Chem. Abstr. 2001, 134, 131319).
2001WOP23368 J. Vermehren, E. Schmidt, M. J. Ford, R. W. G. Foster, I. A. Bourne, PCT Int. Appl. (World
Intellectual Property Pat. Appl.) WO 01 23,368 (2001) (Chem. Abstr. 2001, 134, 266328).
2001ZN(B)306 W. Petz, B. Neumüller, J. Lorberth, K. Megges, W. Massa, Z. Naturforsch., Teil B 2001, 56,
306–314.
2002BCJ567 K. Ohkata, T. Yano, S. Kojima, Y. Hirada, T. Yoshii, M. Hori, Bull. Chem. Soc. Jpn. 2002, 75,
567–574.
2002BCJ851 F. M. Moghaddam, M. G. Dekamin, M. S. Khajavi, S. Jalili, Bull. Chem. Soc. Jpn. 2002, 75,
851–852.
2002CEJ3872 J. Ruiz, F. Marquínez, V. Riera, M. Vivanco, S. Carcía-Granda, M. R. Díaz, Chem. Eur. J. 2002, 8,
3872–3878.
2002CC1840 D. J. Mindiola, G. L. Hillhouse, J. Chem. Soc., Chem. Commun. 2002, 1840–1841.
2002CPB1223 J. Kaur, N. N. Ghosh, A. Talwar, R. Chandra, Chem. Pharm. Bull. 2002, 50, 1223–1228.
2002CPB1379 A. R. Hergueta, M. J. Figueira, C. López, O. Caamaño, F. Fernández, J. E. Rodríguez-Borges,
Chem. Pharm. Bull. 2002, 50, 1379–1382.
2002EJO301 N. Graf v. Keyserlingk, J. Martens, Eur. J. Org. Chem. 2002, 301–308.
 Functions Containing a Carbonyl Group and Two Heteroatoms 491

2002GC269 N. Nagaraju, G. Kuriakose, Green Chem. 2002, 4, 269–271.

2002GEP10035011 J. Scherer, A. Klausener, R. Soellner, Ger. Pat. DE 10,035,011 (2002) (Chem. Abstr. 2002, 136,
151167).
2002H(57)1799 A. R. Katritzky, X. Cai, V. Y. Vvedensky, B. V. Rogovoy, B. Forood, N. Herbert, Heterocycles
2002, 57, 1799–1806.
2002HAC63 J. Huang, H. Chen, R. Chen, Heteroatom Chem. 2002, 13, 63–71.
2002HAC199 Y. A. Ammar, M. M. Ghorab, A. M. Sh. El-Sharief, Sh. I. Mohamed, Heteroatom Chem. 2002, 13,
199–206.
2002HCA1999 E. Juaristi, M. Hernández-Rodríguez, H. López-Ruiz, J. Aviña, O. Muñoz-Muñiz, Helv. Chim. Acta
2002, 85, 1999–2008.
2002HCA2458 S. Aggarwal, N. N. Ghosh, R. Aneja, H. Joshi, R. Chandra, Helv. Chim. Acta 2002, 85, 2458–2462.
2002HCO123 P. Bílek, J. Slouka, Heterocycl. Commun. 2002, 8, 123–128.
2002HCO321 D. Geffken, S. Zilz, Heterocycl. Commun. 2002, 8, 321–324.
2002ICA204 J. Chen, R. J. Angelici, Inorg. Chim. Acta 2002, 334, 204–212.
2002IS210 J. K. Kong, C. A. Wright, D. L. Delaet, C. P. Kubiak, Inorg. Synth. 2002, 33, 210–211.
2002JA5628 R. D. Adams, B. Captain, W. Fu, M. D. Smith, J. Am. Chem. Soc. 2002, 124, 5628–5629.
2002JA9060 K. S. Feldman, J. C. Saunders, J. Am. Chem. Soc. 2002, 124, 9060–9061.
2002JA9356 T. Moriuchi, T. Tamura, T. Hirao, J. Am. Chem. Soc. 2002, 124, 9356–9357.
2002JAP(K)212160 M. Maruo, K.Saito, T. Soejima, J. Yoda, T. Yoshida, T. Nakajima, Jpn. Kokai JP 2002 212,160
(2002) (Chem. Abstr. 2002, 137, 109061).
2002JCA255 D. K. Mukherjee, C. R. Saha, J. Catal. 2002, 210, 255–262.
2002JCA548 F. Shi, Y. Deng, J. Catal. 2002, 211, 548–551.
2002JCO175 A. Nefzi, M. Giulianotti, L. Truong, S. Rattan, J. M. Ostresh, R. A. Houghten, J. Comb. Chem.
2002, 4, 175–178.
2002JCO285 A. R. Katritzky, V. Vvedensky, B. V. Rogovoy, K. Kovalenko, E. Torres, B. Forood, J. Comb.
Chem. 2002, 4, 285–289.
2002JCO320 B. Raju, N. Nguen, G. W. Holland, J. Comb. Chem. 2002, 4, 320–328.
2002JCO345 G. Klein, A. N. Acharya, J. M. Ostresh, R. A. Houghten, J. Comb. Chem. 2002, 4, 345–351.
2002JCO436 O. Shimomura, B. Clapham, C. Spanka, S. Mahajan, K. D. Janda, J. Comb. Chem. 2002, 4,
436–441.
2002JCO484 Y. Yu, J. M. Ostresh, R. A. Houghten, J. Comb. Chem. 2002, 4, 484–490.
2002JCO491 C. W. Phoon, M. M. Sim, J. Comb. Chem. 2002, 4, 491–495.
2002JCR(S)213 G. Mekuskiene, S. Tumkevicius, P. Vainilavicius, J. Chem. Res. (S) 2002, 213–215.
2002JCS(P1)1877 M. J. Wanner, G.-J. Koomen, J. Chem. Soc., Perkin Trans. 1 2002, 1877–1880.
2002JCS(P1)1982 D. D. Long, M. D. Smith, A. Martin, J. R. Wheatley, D. G. Watkins, M. Müller, G. W. J. Fleet, J.
Chem. Soc., Perkin Trans. 1 2002, 1982–1998.
2002JHC417 M. F. Braña, C. Guisado, J. Pérez-Castells, L. Pérez-Serrano, J. Heterocycl. Chem. 2002, 39,
417–420.
2002JHC989 G. Lukás, G. Simig, J. Heterocycl. Chem. 2002, 39, 989–996.
2002JMC2942 J. L. Romine, S. W. Martin, V. K. Gribkoff, C. G. Boissard, S. I. Dworetzky, J. Natale, Y. Li,
Q. Gao, N. A. Meanwell, J. E. Starrett, Jr., J. Med. Chem. 2002, 45, 2942–2952.
2002JMC2994 J. Regan, S. Breitfelder, P. Cirillo, T. Gilmore, A. G. Graham, E. Hickey, B. Klaus, J. Madwed,
M. Moriak, N. Moss, C. Pargellis, S. Pav, A. Proto, A. Swinamer, L. Tong, C. Torcellini, J. Med.
Chem. 2002, 45, 2994–3008.
2002JMC5448 G. D. Brown, S. K. Luthra, C. S. Brock, M. F. G. Stevens, P. M. Price, F. Brady, J. Med. Chem.
2002, 45, 5448–5457.
2002JOC3 M. Gravel, K. A. Thompson, M. Zak, C. Bérubé, D. G. Hall, J. Org. Chem. 2002, 67, 3–15.
2002JOC3687 T. Kihlberg, F. Karimi, B. Långström, J. Org. Chem. 2002, 67, 3687–3692.
2002JOC4086 F. Qian, J. E. McCusker, Y. Zhang, A. D. Main, M. Chlebowski, M. Kokka, L. McElwee-White, J.
Org. Chem. 2002, 67, 4086–4092.
2002JOC5527 M. Seki, Y. Mori, M. Hatsuda, S.-i. Yamada, J. Org. Chem. 2002, 67, 5527–5536.
2002JOC5546 A. M. Dias, I. Cabral, M. F. Proença, B. L. Booth, J. Org. Chem. 2002, 67, 5546–5552.
2002JOC8010 B. Cosimelli, V. Frenna, S. Guernelli, C. Z. Lanza, G. Macaluso, G. Petrillo, D. Spinelli, J. Org.
Chem. 2002, 67, 8010–8018.
2002JOC8827 R. Wieboldt, D. Ramesh, E. Jabri, P. A. Karplus, B. K. Carpenter, G. P. Hess, J. Org. Chem. 2002,
67, 8827–8831.
2002JOC9070 C.-C. Tai, M. J. Huck, E. P. McKoon, T. Woo, P. G. Jessop, J. Org. Chem. 2002, 67, 9070–9072.
2002JOM(646)247 E. Leiner, M. Scheer, J. Organomet. Chem. 2002, 646, 247–254.
2002JOM(657)48 Y. Endo, C. Songkram, R. Yamasaki, A. Tanatani, H. Kagechika, K. Takaishi, K. Yamaguchi, J.
Organomet. Chem. 2002, 657, 48–58.
2002JOM(658)117 K.-B. Shiu, J.-Y. Chen, G.-H. Lee, F.-L. Liao, B.-T. Ko, Y. Wang, S.-L. Wang, C.-C. Lin, J.
Organomet. Chem. 2002, 658, 117–125.
2002JOM(658)147 V. A. Ershova, A. V. Golovin, V. M. Pogrebnyak, J. Organomet. Chem. 2002, 658, 147–152.
2002JOU602 Z. Turgut, N. Öcal, Russ. J. Org. Chem. (Engl. Transl.) 2002, 38, 602–605.
2002M1067 C. O. Usifoh, L. O. Okunrobo, Monatsh. Chem. 2002, 133, 1067–1070.
2002MI81 D. M. Whitehead, T. Jackson, S. C. McKeown, A. Routledge, React. Funct. Polym. 2002, 52,
81–87.
2002MI109 S. B. Naik, V. Joshi, Indian J. Heterocycl. Chem. 2002, 12, 109–112.
2002MI239 C.-Y. Chiu, C.-N. Kuo, W.-F. Kuo, M.-Y. Yeh, J. Chin. Chem. Soc. 2002, 49, 239–249.
2002MI267 F. Paul, J. Fisher, P. Ochsenbein, J. A. Osborn, C. R. Chimie 2002, 5, 267–287.
492 Functions Containing a Carbonyl Group and Two Heteroatoms

2002MI673 N. A. Ovchinnikova, A. E. Sinyakov, A. M. Reznik, S. G. Sakharov, Yu. E. Gorbunova,

Yu. N. Mikhailov, A. S. Kanishcheva, V. D. Butskii, Russ. J. Coord. Chem. (Engl. Transl.) 2002,
28, 673–677.
2002MI785 J. F. Eggler, C. A. Gabel, K. Zandi, J. D. Weaver, H. McKechney, M. A. Dombroski, H. Peurano,
N. Hawryluk, J. Label. Cpd. Radiopharm. 2002, 45, 785–794.
2002MI963 V. A. Ershova, A. V. Virovets, V. M. Pogrebnyak, A. V. Golovin, Inorg. Chem. Commun. 2002, 5,
963–965.
2002OL597 T. Morgan, N. C. Ray, D. M. Parry, Org. Lett. 2002, 4, 597–598.
2002OL4033 T. Y. H. Wu, P. G. Schultz, Org. Lett. 2002, 4, 4033–4036.
2002OL4639 L. Siracusa, F. M. Hurley, S. Dresen, l. J. Lawless, M. N. Pérez-Payán, A. P. Davis, Org. Lett.
2002, 4, 4639–4642.
2002OL4673 M. D. McReynolds, K. T. Sprott, P. R. Hanson, Org. Lett. 2002, 4, 4673–4676.
2002OM3108 U. Burckhardt, G. L. Casty, J. Gavenonis, T. D. Tilley, Organometallics 2002, 21, 3108–3122.
2002OM4847 R. D. Adams, B. Qu, M. D. Smith, Organometallics 2002, 21, 4847–4852.
2002PS(177)1303 V. Lachkova, S. Varbanov, G. Hägele, H. Keck, T. Tosheva, Phosphorus, Sulfur Silicon Relat.
Elem. 2002, 177, 1303–1313.
2002SC803 G. H. Lee, H. W. Lee, C. S. Pak, Synth. Commun. 2002, 32, 803–812.
2002SC2613 Z. Li, Y. Zhang, Synth. Commun. 2002, 32, 2613–2618.
2002SC3373 X. Wang, Z. Li, Z. Guo, Synth. Commun. 2002, 32, 3373–3381.
2002SL1779 N. Tewari, R. C. Mishra, V. K. Tiwari, R. P. Tripathi, Synlett 2002, 1779–1782.
2002T4225 K. Van Emelen, T. De Wit, G. J. Hoornaert, F. Compernolle, Tetrahedron 2002, 58, 4225–4236.
2002T7207 V. Stastny, P. Lhoták, V. Michlová, I. Stibor, J. Sykora, Tetrahedron 2002, 58, 7207–7211.
2002TL4313 Ó. López, I. Maya, V. Ulgar, I. Robina, L. Fuentes, J. G. Fernández-Bolaños, Tetrahedron Lett.
2002, 43, 4313–4316.
2002TL6431 S. Man, P. Kulhánek, M. Potáček, M. Nečas, Tetrahedron Lett. 2002, 43, 6431–6433.
2002TL6649 N. I. Vasilevich, D. H. Coy, Tetrahedron Lett. 2002, 43, 6649–6652.
2002WOP66442 Z. Tan, J. J. Song, PCT Int. Appl. (World Intellectual Property Pat. Appl.) WO 02 66,442 (2002)
(Chem. Abstr. 2002, 137, 185488).
2002WOP83642 S. Breitfelder, P. F. Cirillo, J. R. Regan, PCT Int. Appl. (World Intellectual Property Pat. Appl.)
WO 02 83,642 (2002) (Chem. Abstr. 2002, 137, 325421).
2002ZN(B)937 T. Fricke, A. Dickmans, U. Jana, M. Zabel, P. G. Jones, I. Dix, B. König, R. Herges,
Z. Naturforsch., Teil B 2002, 57, 937–945.
2003CC486 B. Gabriele, R. Mancuso, G. Salerno, M. Costa, J. Chem. Soc., Chem. Commun. 2003, 486–487.
2003CRV3707 E. Cariati, D. Roberto, R. Ugo, Chem. Rev. 2003, 103, 3707–3732.
2003JCO155 C. E. Hoesl, A. Nefzi, R. A. Houghten, J. Comb. Chem. 2003, 5, 155–160.
2003JCO632 J. K. Cho, P. D. White, W. Klute, T. W. Dean, M. Bradley, J. Comb. Chem. 2003, 5, 632–636.
2003JMC113 S. Sasaki, N. Cho, Y. Nara, M. Harada, S. Endo, N. Suzuki, S. Furuya, M. Fujino, J. Med. Chem.
2003, 46, 113–124.
2003JMC1112 Y.-Q. Wu, S. Belyakov, C. Choi, D. Limburg, B. E. Thomas IV, M. Vaal, L. Wei, D. E. Wilkinson,
A. Holmes, M. Fuller, J. McCormick, M. Connolly, T. Moeller, J. Steiner, G. S. Hamilton, J. Med.
Chem. 2003, 46, 1112–1115.
2003JMC3758 R. Gitto, V. Orlando, S. Quartarone, G. De Sarro, A. De Sarro, E. Russo, G. Ferreri, A. Chimirri,
J. Med. Chem. 2003, 46, 3758–3761.
2003JMOC(A)135 J. Mei, Y. Yang, Y. Xue, S. Lu, J. Mol. Catal. A 2003, 191, 135–139.
2003JOC754 N. A. Magnus, P. N. Confalone, L. Storace, M. Patel, C. C. Wood, W. P. Davis, R. L. Parsons, Jr.,
J. Org. Chem. 2003, 68, 754–761.
2003JOC1615 K.-G. Hilton, A. D. Main, L. McElwee-White, J. Org. Chem. 2003, 68, 1615–1617.
2003JOC1626 G. R. Krow, W. S. Lester, G. Lin, Y. Fang, P. J. Carroll, J. Org. Chem. 2003, 68, 1626–1629.
2003JOC5512 H. Li, J. L. Petersen, K. K. Wang, J. Org. Chem. 2003, 68, 5512–5518.
2003JOM(669)44 E. Lucenti, E. Cariati, C. Dragonetti, D. Roberto, J. Organomet. Chem. 2003, 669, 44–47.
2003MI425 T. Sun, J. Li, Y.-L. Wang, J. Chin. Chem. Soc. 2003, 50, 425–427.
2003OL2555 W. Zhang, Y. Li, Org. Lett. 2003, 5, 2555–2558.
2003PS(178)61 I. Mohammadpoor-Baltork, M. M. Sadeghi, K. Esmayilpour, Phosphorus, Sulfur Silicon Relat.
Elem. 2003, 178, 61–65.
2003SC1449 S. Wang, B. Shi, Y. Li, Q. Wang, R. Huang, Synth. Commun. 2003, 33, 1449–1457.
2003T1731 N. V. Lyutenko, I. I. Gerus, A. D. Kacharov, V. P. Kukhar, Tetrahedron 2003, 59, 1731–1738.
2003TL591 I. Mohammadpoor-Baltork, M. M. Khodaei, K. Nikoofar, Tetrahedron Lett. 2003, 44, 591–594.
2003TL811 D. Fattori, P. D’Andrea, M. Porcelloni, Tetrahedron Lett. 2003, 44, 811–814.
2003TL2065 W. Zhang, C. H.-T. Cheng, T. Nagashima, Tetrahedron Lett. 2003, 44, 2065–2068.
 Functions Containing a Carbonyl Group and Two Heteroatoms 493

Biographical sketch

Olga Denisko was born in Krasnoyarsk, Russia and studied at Moscow

State University, Russia, where she obtained her Ph.D. in 1993 under
the direction of Professor N. S. Zefirov. During 1994–1996, she worked
as a Postdoctoral Research Fellow in the Center for Heterocyclic Com-
pounds, University of Florida, FL under supervision of Professor
A. R. Katritzky, after which she returned to Russia and was employed
as a Chemist in the Central Laboratory of ‘‘Krasfarma’’ Pharmaceuticals
(Krasnoyarsk, Russia). In 1998, she returned to the University of Florida
as Postdoctoral Research Fellow/Group Leader. After working there
for another two years, she was employed as a Senior Research Chemist
by Alchem Laboratories (Alachua, FL). In June 2002, she took up her
present position as Assistant Scientific Information Analyst at the Che-
mical Abstracts Service, Columbus, OH. Her scientific research interests
include various aspects of heterocyclic organic chemistry and chemistry
of organosulfur compounds.

# 2005, Elsevier Ltd. All Rights Reserved Comprehensive Organic Functional Group Transformations 2
No part of this publication may be reproduced, stored in any retrieval system ISBN (set): 0-08-044256-0
or transmitted in any form or by any means electronic, electrostatic, magnetic
tape, mechanical, photocopying, recording or otherwise, without permission Volume 6, (ISBN 0-08-044258-7); pp 453–493
in writing from the publishers