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C(sp2)-C(sp) and C(sp)-C(sp) Coupling Reactions Catalyzed by Oxime-Derived Palladacycles

Diego A. Alonso, Carmen Najera,* Ma Carmen Pacheco
Departamento de Qumica Organica, Universidad de Alicante, Apartado 99, 03080 Alicante, Spain Fax: ( 34)-965903549, e-mail: [email protected]

Received: April 10, 2003; Accepted: June 23, 2003

Abstract: Oxime-derived chloro-bridged palladacycle 8a, derived from 4,4'-dichlorobenzophenone, is an efficient pre-catalyst for the copper- and amine-free Sonogashira coupling between terminal acetylenes and aryl iodides and aryl and vinyl bromides achieving turnover numbers (TON) of up to 72000. Catalyst 8a has also been shown as a effective promoter for the sila-Sonogashira coupling between 1-(trimethylsilyl)alkynes and aryl iodides and bromides in the presence of CuI or Bu4NBr as co-catalysts. This complex also catalyzes efficiently the homocoupling

reaction (Glaser-type coupling) between 1-alkynes in NMP at room temperature with TONs of up to 1000. All the reactions can be performed under air and employing reagent-grade chemicals under very low loading conditions, which demonstrates the versatility and high activity of oxime-derived palladacycles. Keywords: alkynes; aryl halides; CC coupling; homogeneous catalysis; metallacycles; N ligands; palladium

Introduction
Metal-catalyzed acetylenic homo- and cross-coupling processes are currently under intensive study due to the presence of the alkynyl moieties in a wide range of natural and unnatural organic materials.[1] Two of the most useful synthetic transformations of alkynes are the SonogashiraHagihara reaction[2] (palladium/coppercatalyzed cross-coupling reactions of sp2-C to sp-C atoms) or the silane version of the process employing alkynylsilanes (sila-Sonogashira reaction[3]), and the palladium-catalyzed acetylenic oxidative homocoupling reaction between their sp-carbon atoms, called the Glaser-type process.[4] The Sonogashira coupling of terminal acetylenes with sp2-C atoms, provides a useful tool for the preparation of alkyl-, aryl-, and diaryl-substituted acetylenes (Eq. 1, R2 H). The reaction is typically carried out in the presence of copper(I) salts as co-catalysts, and employing amines as solvents. Most frequently, high loadings of palladium (0.1 5 mol %) and varying amounts of CuI are required when typical catalysts such as Pd(PPh3)2Cl2, Pd(PPh3)4 or Pd2(dba)3 are employed. With respect to

the methodologies that employ CuI as co-catalyst, Buchwald and Fu,[5] have described Pd(PhCN)2Cl2/ CuI/P(t-Bu)3 as a versatile catalyst system for the Sonogashira reaction of aryl bromides at room temperature (TON up to 200). Using an excess of a bulky and electron-donating ligand such as P(t-Bu)3 (6 mol %) and a high catalyst loading (3 mol % of Pd), these authors could effect the Sonogashira coupling using only an equimolar amount of amine. On the other hand, Mori has carried out the Sonogashira coupling of terminal alkynes with aryl iodides and bromides at room temperature in the presence of Pd(PPh3)2Cl2 in THF with aqueous ammonia as base.[6] Very recently, Plenio and colleagues[7] have presented a new and very efficient catalytic system for the Sonogashira coupling of activated and non-activated aryl chlorides with terminal acetylenes, based on the combination Na2PdCl4/(1Ad)2PBn/CuI (1-Ad 1-adamantyl, Bn benzyl). On the other hand, N-heterocyclic carbene palladium(II) complex 1,[8] has also been shown to mediate the Sonogashira coupling of aryl bromides with different alkynes at 80 0C in DMF under inert atmosphere, in the presence of 2 mol % of CuI and 1 mol % of PPh3. However, and in order to simplify the reaction protocol, copper-free methodologies have lately attracted most attention, as the use of copper(I) salts as co-catalysts usually induces the homocoupling reaction (Glasertype[4]) of terminal alkynes to diynes in the presence of oxygen as well as the precipitation of catalytically inactive palladium black. Recent advances in this topic have been reported employing amines as solvents
DOI: 10.1002/adsc.200303067
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cally diarylated acetylenes employing either trimethylsilylacetylene (TMSA) or bis(trimethylsilyl)acetylene (BTMSA), which avoids the use of the toxic and tricky to handle acetylene. The sila-Sonogashira reaction is usually carried out in the presence of a palladium catalyst and a fluoride ion source as activator,[18] because trimethylsilylated alkynes are usually inert to the SonogashiraHagihara reaction conditions. Lately, silver(I) salts have been shown as very effective cocatalysts for the coupling of aryl iodides or vinyl triflates with alkynylsilanes, employing different Pd(II) or Pd(0) catalysts accompanied by phosphane ligands.[19] Mori and co-workers have also shown that CuCl is a very effective co-catalyst for the palladium-catalyzed reaction of 1-trimethylsilylalkynes with aryl triflates in DMF at 80 8C and under neutral conditions.[20] Yang and Nolan have recently reported a very efficient sila-Sonogashira reaction between aryl bromides and alkynylsilanes catalyzed by the system Pd(OAc)2/imidazolium salt 6 (Figure 1).[21] Finally, Grieco et al. have used the system PdCl2(PPh3)2/CuI in the presence of an amidine such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as base, for the one-pot synthesis of symmetrical and unsymmetrical bisarylethynes employing TMSA under aqueous conditions.[22] Acetylenic homocoupling of terminal alkynes[4] (Glaser reaction), is an atom economic and straightforward method for the synthesis of conjugated diynes, polyynes and acetylenic arrays. These derivatives are finding increasing applications as key structural elements of new materials with unusual electrical and optical properties, and are encountered in numerous natural and biologically active compounds. Since Rossi in 1985 optimized the homocoupling reaction of terminal alkynes as a synthetic method, employing palladium as catalyst in the presence of CuI as co-catalyst and chloroacetone as terminal oxidant,[23] diverse modifications of the procedure have appeared using different oxidants such as DMSO,[24] iodine[25] or (diacetoxy)iodobenzene.[26] Palladium(II) complexes bearing N-heterocyclic carbenes modified with phosphines of the type 7 (Figure 1), have also been found to promote the homocoupling of phenylacetylene in the presence of CuI as co-catalyst and TEA as solvent even in the absence of added oxidant.[27] However, there are no reported examples, to the best of our knowledge, about the use of palladacycles as catalysts for the homocoupling reaction of terminal acetylenes. We have recently reported that phosphane-free oxime-based palladacycles 8 (Figure 1), are air- and water-stable pre-catalysts for a wide range of crosscoupling processes such as Heck, Suzuki, Stille, Sonogashira and Ullmann-type reactions in organic[28] and aqueous solvents.[29] In a preliminary communication,[28d] we have shown complexes 8 as very efficient and versatile catalysts for amine- and copper-free Sonogashira-type reactions of aryl iodides and aryl
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Figure 1.

(piperidine or pyrrolidine) and palladium(0) complexes such as Pd(PPh3)4 as catalysts.[9] On the other hand, Herrmann and co-workers have recently found that the catalytic system Pd2(dba)3/P(t-Bu)3 promotes the copper-free Sonogashira-type reaction of aryl bromides at room temperature.[10] Likewise, stoichiometric amounts of silver(I) oxide for aryl iodides, and tetrabutylammonium fluoride (Bu4NF) or tetrabutylammonium hydroxide (Bu4NOH) for aryl bromides, have also been used as activators in the first described copper- and amine-free procedure,[11] even though when using the ammonium salts as activators, the coupling reaction is rather sluggish and CuI has to be added in a further improved procedure.[12] With respect to the use of palladacycles[13] as pre-catalysts for the copper-free Sonogashira-type reaction, Herrmanns phosphapalladacycle 2[14] and carbene-derived palladacycles 3[15] and 4[16] (Figure 1), have been used in a copper-free protocol employing triethylamine (TEA) as solvent at 90 8C with turnover numbers (TON) of up to 8000 when using catalyst 2. With regard to the use of aryl chlorides as sp2 counterparts of the reaction, Eberhard et al.[17] have established the first efficient palladium-based and copper-free catalytic system, which cross-couples efficiently a wide range of activated and non-activated aryl chlorides with phenylacetylene, employing the palladium PCP pincer complex 5 (Figure 1) in the presence of catalytic amounts of ZnCl2. The use of alkynylsilanes as sp components in the palladium-catalyzed cross-coupling reaction (sila-Sonogashira coupling3) (Eq. 1, R2 SiR3), has become a very important tool in synthetic organic chemistry. This protocol has been used for the synthesis of symmetriAdv. Synth. Catal. 2003, 345, 1146 1158

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bromides with a variety of terminal acetylenes in air and using reagent-grade chemicals with turnover numbers of up to 72000. Herein, we report the full account of oximederived complexes as efficient pre-catalysts not only for the palladium-catalyzed Sonogashira-type coupling, but also for the sila-Sonogashira and homocoupling reactions of acetylenes under air atmosphere. We describe first the copper- and amine-free Sonogashira-type coupling of aryl iodides and vinyl and aryl bromides with different terminal acetylenes in N-methylpyrrolidinone (NMP) as solvent and tetrabutylammonium acetate (Bu4NOAc) as base. Secondly, the synthesis of symmetrical diarylethynes from the palladium cross-coupling reaction of TMSA or BTMSA with aryl iodides and bromides in the presence of CuI as co-catalyst is studied, as well as the synthesis of monoarylated trimethylsilylalkynes from the palladium cross-coupling reaction of TMSA or BTMSA with aryl iodides and bromides in the presence of tetrabutylammonium bromide (Bu4NBr) as co-catalyst. Finally, the palladium-catalyzed homocoupling reaction of terminal alkynes at room temperature in NMP as solvent and pyrrolidine as base to afford symmetrical conjugated diynes will be considered.

Diego A. Alonso et al.

Results and Discussion

Sonogashira-type Coupling of Aryl and Vinyl Halides with Terminal Alkynes The alkynylation reaction of aryl halides was evaluated with an oxime catalyst derived from 4,4'-dichloroben-

zophenone 8a. Other palladacycles under study in our group, derived from benzophenone, acetophenone, pinacolone and 4,4'-dimethoxybenzophenone oximes, all gave in general similar or inferior results. In order to determine the optimum reaction conditions, we chose the coupling between 1-chloro-4-iodobenzene and phenylacetylene in the presence of catalyst 8a (0.1 0.5 mol % of Pd) as a model reaction (Scheme 1, Table 1). As we have previously reported,[28d] the coupling reaction, provided a good yield of the arylated acetylene 9a after 1 h (84%) when pyrrolidine was used as solvent in the presence of CuI as co-catalyst (5 mol %) at 90 8C under air using 0.5 mol % of Pd (Table 1, entry 1). Unexpectedly, when using NMP as solvent and only 2 equiv. of pyrrolidine as base in the absence of CuI at 110 8C (Table 1, entry 2), an excellent 96% yield of product was obtained. As a consequence of this result, we carried out a base study, which showed that inorganic bases such as NaOAc or NH4OAc (150 mol %), only led to poor reaction yields (Table 1, entries 3 and 4). Other bases such as tetrabutylammonium fluoride (Bu4NF) (150 mol %), gave an acceptable 86% yield after 3 h. Aqueous tetrabutylammonium hydroxide (Bu4NOH) did not promote the reaction coupling at all (Table 1, entry 6). However, tetrabutylammonium acetate (Bu4NOAc, 150 mol %) showed the best activity even when the catalyst loading was reduced to 0.1 mol % of Pd (Table 1, entry 7) and also in the presence of small amounts of water (Table 1, entry 8). The reaction could be carried out at lower temperature (80 0C) and using 1.1 equiv. of Bu4NOAc as well (Table 1, entry 9). Changing the solvent from NMP to THF under reflux, resulted in a lower yield and longer reaction times (Table 1, en-

Table 1. Sonogashira coupling: reaction conditions study. Entry 1 2 3 4 5 6 7 8 9 10 11 12

[a] [b] [c] [d] [e] [f]

Solvent Pyrrolidine NMP NMP NMP NMP NMP NMP NMP/H2O, 95/5 NMP THF NMP NMP

Additive [mol %] CuI (5) Pyrrolidine[d] NaOAc[e] NH4OAc[e] Bu4NF (150) Bu4NOH (150) Bu4NOAc (150) Bu4NOAc (110) Bu4NOAc (110) Bu4NOAc (110) Bu4NOAc (110) Bu4NOAc (110)

T[a] [0C] 90 110 110 110 110 110 110 110 80 -[g] 110 110

8a [mol % Pd] 0.5 0.5 0.5 0.5 0.5 0.1 0.1 0.1 0.1 0.1 102 103

t [h] 1 1 1 3.5 3 3 2 1 4 5 24 24

Yield[b] [%] 84 96 36[f] 29[f] 86[f] 0 > 99 > 99 > 99 89 97 72

TON[c] 168 192 72 58 172 990 990 990 890 9700 72000

[g]

Bath temperature. Conversion determined by GLC using decane as internal standard and based on starting 1-chloro-4-iodobenzene. TON turnover number (mol product mol Pd1). 2 equiv. were used. 1.5 equiv. were used. Several non-identified enyne by-products were also obtained in variable yields as a result of the addition of the terminal alkyne to the reaction product. Under THF reflux.
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preparation of silylated alkynes (Table 2, entries 2 and 8), as trimethylsilylacetylene (TMSA), always gave variable amounts of the sila-Sonogashira products. In the case of employing 2-propyn-1-ol as the sp-counterpart (Table 2, entry 5), a 60% isolated yield of the corresponding alcohol 9e was obtained together with a 10% yield of the acetylated compound 9e. As illustrated in entries 7 and 8, the less reactive, electron-rich 4iodoanisole also coupled with similar good efficiency. Steric effects as in 2-iodotoluene (Table 2, entry 9), did not influence the yield of the reaction. N-Acetyl-oiodoaniline, gave the alkylynated product 9j in 65% isolated yield. These types of substrates have been used in indole synthesis,[30] though in our case, no traces of cyclization product were observed (Table 2, entry 10). We also found that an excess of 1-octyne reacted with

Scheme 1.

try 10). Higher TONs, 9700 and 72000, accompanied with very good yields could be obtained at 110 8C, when the catalyst loading was reduced to 102 and 103 mol % of Pd, respectively (Table 1, entries 11 and 12). Using NMP as solvent and Bu4NOAc as base, complex 8a catalyzed the Sonogashira coupling of a wide variety of aryl iodides with terminal acetylenes to afford the corresponding arylated alkynes 9 (Scheme 2, X I, Table 2). Reaction conversions (determined by GLC using decane as internal standard), were generally high after short reaction times for all type of substrates, and the chromatographic purification of the compounds were carried out using either silica gel or florisil. Activated substrates such as 1-chloro-4-iodobenzene reacted with an array of aromatic and aliphatic alkynes in good to excellent yields (Table 2, entries 1 5). (Triisopropylsilyl)acetylene had to be used for the

Scheme 2.

Table 2. Sonogashira-type coupling of aryl iodides catalyzed by 8a. Entry Aryl iodide Alkyne 8a [mol % Pd] T[a] [0C] t [h] Product No. 1 2 3 4 5 6 7 8 9 10 11 0.1 0.5 0.5 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 110 110 110 110 110 110 110 110 110 110 110 1 1 1 5 1 1 1 1 1 2 4 9a 9b 9c 9d 9e 9f 9g 9h 9i 9j 9k Yield[b, c] [%] > 99 (73) > 99 100 [76] 85 (60) 99 (60)[d] > 99 [88] 89 [80] 90 92 (80) 100 (65) 80[e, f]

[a] [b]

[c] [d] [e] [f]

Bath temperature. Determined by GLC, based on ArI using decane as internal standard. In parenthesis isolated yield after flash chromatography. In brackets isolated yield after florisil chromatography. Reaction conditions: ArI (0.5 mmol), alkyne (0.6 mmol), Bu4NOAc (0.55 mmol), 8a, NMP (2 mL ). 10% of acetylated alcohol, 9e, was also obtained Reaction conditions: ArI (0.5 mmol), alkyne (1.2 mmol), Bu4NOAc (1.1 mmol), 8a, NMP (2 mL ). 14% of monoalkynylated compound, 9k, was also obtained.
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Table 3. Sonogashira coupling of aryl and vinyl bromides catalyzed by 8a. Entry ArBr Alkyne 8a [mol % Pd] T[a] [0C] t [h]

Diego A. Alonso et al.

Product No. Yield[b, c] [%] 93 (90)[d] 78 66 (40) 96 (75) 81 79 96 81 85 45 [30] 89 (39) [52][f, g] 73 (58)[f, h] 75 [60][f, i] 86 [73][j, k]

1 2 3 4 5 6 7 8 9 10 11 12 13 14

0.5 0.1 0.1 0.1[e] 0.1 0.1 0.1 0.25 0.25 0.1 0.1 0.1 0.1 0.1

110 110 110 110 110 110 110 130 130 110 130 110 110 110

7.5 2 7 1 1 3.5 1 4 1 3 23 7.5 3 29

9a 9b 9l 9m 9n 9o 9p 9q 9h 9r 9s 9t 9k 9u

15 16
[a] [b]

0.1 0.1

110 110

3 1

9v 10

85 (40) [62] 63 (36)

[c] [d] [e] [f] [g] [h] [i] [j] [k]

Bath temperature. Determined by GLC, based on ArBr using decane as internal standard. In parenthesis isolated yield after flash chromatography. In brackets isolated yield after florisil chromatography. Reaction conditions: ArBr (0.5 mmol), alkyne (0.6 mmol), Bu4NOAc (0.55 mmol), 8a, NMP (2 mL ). In parenthesis crude yield after work-up (pure by 1H and 13C NMR ). 2.5 equiv. of 1-octyne were used. Reaction conditions: ArBr (0.5 mmol), alkyne (1.5 mmol), Bu4NOAc (1.2 mmol), 8a, NMP (2 mL ). 11% of pure monoalkynylated compound, 9 s, was also obtained. 17% of pure monoalkynylated compound, 9 t, was also obtained. 25% of pure monoalkynylated compound, 9k, was also obtained. Reaction conditions: ArBr (0.5 mmol), alkyne (2.5 mmol), Bu4NOAc (2.5 mmol), 8a, NMP (2 mL ). 14% and 2% of pure di- and monoalkynylated compounds, 9u and 9u were also obtained, respectively

fairly good yield with 1,2-diiodobenzene to afford the bis-Sonogashira coupling product 9k (Table 2, entry 11). In order to evaluate the scope of this methodology, we also examined the Sonogashira-type coupling of diverse aryl bromides with alkyl- and aryl-substituted alkynes (Scheme 2, X Br, Table 3). Activated substrates such as 1-chloro-4-bromobenzene, 1-bromo-4-(trifluoromethyl)benzene and 1-bromonaphthalene reacted with phenylacetylene and 1-octyne in good yields (Table 3, entries 1 4). 9-Bromoanthracene, reacted with phenyl1150 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

acetylene and (triisopropylsilyl)acetylene to afford, in high yields (Table 3, entries 5 and 6), the corresponding 9-alkynylanthracenes 9n and 9o with no observable formation of aceanthrylenes.[31] Sterically hindered 2bromobenzonitrile also coupled with fairly good efficiency with phenylacetylene at 110 8C (Table 3, entry 7). However, in the case of less reactive electron-rich aryl bromides such as 4-bromotoluene and 4-bromoanisole, 0.25 mol % of Pd and 130 8C were used to achieve fast conversions (Table 3, entries 8 and 9). 4-Bromobenzalasc.wiley-vch.de
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reaction between aryl halides and silylated alkynes (Scheme 3, Table 4). In initial experiments, a catalytic system consisting of 8a (0.5 mol % of Pd) and CuI (5 mol %) in pyrrolidine as solvent at 90 0C (Method A), was used to achieve with rather good yields the coupling of 1-chloro-4-iodobenzene, 1-naphthalene and 4-iodoanisole with both TMSA (1.2 equiv.) and BTMSA (0.75 equiv.) as synthetic equivalents of acetylene, to afford the corresponding diarylated ethynes 11 (Table 4, entries 1, 2, 6, 7 and 11). The reaction coupling with BTMSA could be carried out with similar levels of efficiency employing NMP as solvent and 3 equiv. of pyrrolidine as base, by just increasing the temperature to 110 8C (Method B) (Table 4, entries 3, 8 and 12). When Bu4NBr, (20 mol %), was used as co-catalyst instead of CuI (Method C), the monosilylated alkynes 12, were isolated as the major products both in the case of using TMSA (Table 4, entries 4, 9 and 13), and BTMSA (Table 4, entries 5, 10 and 14). As depicted in Table 4, entries 15 19, aryl bromides reacted sluggishly with TMSA and BTMSA. Again when using CuI as co-catalyst (Method B, Table 4, entries 16 and 17) diarylated acetylenes 11 were the main reaction products. On the contrary, in the presence of TBAB (Method C) the major products were the monoarylated silylalkynes 12 (Table 4, entries 15, 18 and 19). Consequently, TMSA and BTMSA behaved as acetylene equivalents when the coupling reaction was carried out in the presence of CuI. However, in the absence of CuI, TMSA gave only the Sonogashira coupling products and BTMSA the monosila-Sonogashira products. The catalytic system was also competent for the silaSonogashira coupling of 1-chloro-4-iodobenzene with other silylated alkynes such as 1-phenyl-2-(trimethylsilyl)acetylene and 1-trimethylsilyl-1-pentyne, which gave after 7 h the asymmetrical substituted alkynes 9a and 9w in 76 and 50% yield, respectively, under the conditions of Method B (Scheme 4). With respect to the reaction mechanism, we observed the fast formation of a 1 : 1 mixture of phenylacetylene

dehyde ethylene glycol acetal, gave the corresponding coupling product 9r after reaction with 1-octyne in a moderate 30% isolated yield, with no observable deprotection product (Table 3, entry 10). Polybromobenzenes, such as 1,2-dibromobenzene, 1,4-dibromobenzene and 1,3,5-tribromobenzene, reacted with an excess of the corresponding alkyne (3 or 5 equiv.), affording the resultant products in satisfactory yields (Table 3, entries 11 14). The yield of the corresponding peralkynylated product could not be improved when the amount of alkyne was considerably increased. Heterocyclic 2-bromothiophene was likewise converted efficiently to the corresponding cross-coupling product 9v (Table 3, entry 15). In the case of the vinyl bromide trans-b-bromostyrene, the coupling with (triisopropylsilyl)acetylene, afforded the corresponding trans-enyne 10 after 1 h at 110 8C in a moderate 36% isolated yield (Table 3, entry 16). As described above, moderate to good yields were generally obtained, and these were usually higher when fluorisil was used instead of silica gel in the chromatographic purification of the crude products (see Table 3, entries 11 and 15). The efficiency as catalyst in the Sonogashira-type reaction of oxime-derived palladacycle 8a, is apparent when compared with Herrmanns phosphapalladacycle 2,[14] which only works efficiently when phenylacetylene is used as sp counterpart, even employing triethylamine as solvent.

Sila-Sonogashira Coupling of Aryl Halides with Silylated Alkynes During the course of our studies about the Sonogashira Hagihara coupling of trimethylsilylacetylene (TMSA) with different aryl halides, and contrary to the case of the triisopropylsilyl moiety which remained stable under the reaction conditions (see Tables 2 and 3), we observed the formation, in variable and small amounts, of the corresponding sila-Sonogashira coupling products. We then decided to carry out an investigation of the catalytic activity of complex 8a in the cross-coupling

Scheme 3.

Scheme 4.
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Table 4. Sila-Sonogashira coupling of aryl halides catalyzed by 8a. Entry ArX R 8a[a] [mol % Pd] 0.5 1 0.25 0.5 0.5 0.5 0.5 0.25 0.5 0.5 0.5 0.25 0.5 0.5 0.5 0.25 0.25 0.25 0.5 Method[b] t [h]

Diego A. Alonso et al.

Products No. [ Yield[c] %]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
[a] [b]

TMS H TMS H TMS H TMS TMS H TMS TMS TMS H TMS TMS H TMS TMS TMS

A A B C C A A B C C A B C C C B B C[d] C

3 7 6 2 8 6 8 6 5 21 24 6 5 8 5 24 8 22 8

11a/12a: 61/0 11a/12a: 11a/12a: 11a/12a: 11a/12a: 11b/12b: 84/6 88/0 11/77 11/53 90/0

11b/12b: 99/0 11b/12b: 78/11 11b/12b: 15/61 11b/12b: 11/74 11c/12c: 75/0 11c/12c: 35/10 11c/12c: 5/45 11c / 12c: 0/54 11a/12a: 8/53 11b / 12b: 25/0 11b/12b: 28/6 11b/12b: 22/64 11c/12c: 6/59

[c] [d]

Mol % of Pd with respect to the aryl halide. Method A: ArX (1 mmol), TMSA (1.2 mmol) or BTMSA (0.75 mmol), pyrrolidine (3 mL ), CuI (5 mol %), 90 8C. Method B: ArX (1 mmol), TMSA (0.75 mmol) or BTMSA (0.6 mmol), pyrrolidine (3 mmol), CuI (5 mol %), NMP (2 mL ), 110 8C. Method C: ArX (1 mmol), alkyne (1.2 mmol), pyrrolidine (1 mmol), TBAB (20 mol %), NMP (2 mL ), 110 8C. Determined by GLC, based on ArX using decane as internal standard. The reaction was carried out at 130 8C.

and the corresponding diyne (80% conversion after 30 min.), when 1-phenyl-2-(trimethylsilyl)acetylene was heated in NMP at 110 0C under Method B conditions. However, in the absence of the palladium and copper catalysts, a 36% conversion to phenylacetylene was observed as well after 1 h. This result seems to indicate that the reaction could proceed merely via protodesilylation and coupling of the in situ formed terminal alkyne, though the fact that the desilylation is much faster in the presence of the catalysts (Method B), does not rule out the possibility a simultaneous direct coupling of the silyl alkynes through a transmetallation process. In conclusion, oxime-derived palladacycle 8a, has been shown, to the best of our knowledge, to be the only catalyst of this type that is active in sila-Sonogashira couplings.

Homocoupling Reactions of Terminal Alkynes During the course of our initial studies about the palladium-catalyzed Sonogashira cross-coupling reac1152 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

tion between phenylacetylene and iodobenzene, employing other bases than pyrrolidine as solvent, such as TEA and Hnigs base, in the presence of CuI as cocatalyst,[28a] we found that significant amounts of 1,4diphenylbuta-1,3-diyne were always obtained. Consequently, we also decided to investigate and optimize the ability of catalyst 8a to promote the oxidative homocoupling reaction of different terminal alkynes (Scheme 5, Table 5). As illustrated in Table 5, good isolated yields of conjugated diynes 13 could be obtained by dimerization of 1-alkynes in the presence of oxime-derived catalyst 8a (Scheme 5). We found that complex 8a can effectively promote the coupling of 1-octyne in the presence of CuI (5 mol %) as co-catalyst, using TEA as solvent and pyrrolidine as base (1.1 equiv.) (Table 5, entry 1). As mentioned above for the sila-Sonogashira reaction, catalyst 8a avoids the use of the amine as solvent, and the homocoupling reaction showed even higher levels of effectiveness when the solvent was changed to NMP at 110 8C still employing pyrrolidine as base and under
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Table 5. Homocoupling reactions of terminal alkynes catalyzed by 8a. Product Entry 1 2 3 4 5 6 7 8 9 10 11 12

[a] [b] [c]

R C6H13 C6H13 C7H15 Ph i-Pr3Si C6H13 Me2( OH )C Ph Ph Ph Ph Ph

8a[a] [mol % Pd] 0.5 0.05 0.05 0.05 0.05 0.1 0.05 0.5 0.05 0.05 0.5 0.5

Solvent TEA NMP NMP NMP NMP NMP NMP NMP NMP NMP[e] i-Pr2NH[f] NMP

Base Pyrrolidine Pyrrolidine Pyrrolidine Pyrrolidine Pyrrolidine Bu4NOAc Pyrrolidine Pyrrolidine Pyrrolidine Pyrrolidine TEA[g]

T[b] [0C] 90 110 110 110 110 110 110 rt rt rt rt rt

t [h] 8 3 2 2 2.5 9 23 2 6 6 2 21

No. 13a 13a 13b 13c 13d 13a 13e 13c 13c 13c 13c 13c

Yield[c],[d] [%] 99 99 99 99 90 73 25 99 92 58 87 11 (70) (60) (50) (82) (75)

(80)

[d] [e] [f] [g]

Mol% of Pd with respect to the starting alkyne. Bath temperature. Determined by GLC, based on alkyne using decane as internal standard. In parenthesis isolated yield after flash chromatography. Reaction conditions: alkyne (1 mmol), CuI (5 mol %), base (pyrrolidine, Bu4NOAc or TEA 1.1 mmol.), solvent (2 mL ). The reaction was carried out under Ar atmosphere employing degassed NMP. The reaction was carried out in the presence of 0.5 equiv. of I2. The reaction was carried out in the presence of 1 equiv. of chloroacetone.

lower catalyst loadings (0.05 mol % of Pd, TON 1000) (Table 5, entry 2). Under these conditions, 1-nonyne, phenylacetylene and (triisopropylsilyl)acetylene also gave good yields of the corresponding dialkylated and diarylated diynes 13b, 13c and 13d, respectively (Table 5, entries 3 5). Other bases such as Bu4NOAc lengthened the reaction time and gave lower conversions (Table 5, entry 6). The homocoupling of 2-methyl3-butyn-2-ol (Table 5, entry 7), gave a poor 25% yield of the corresponding homocoupled diol 13e. It is worthy to note that the homocoupling process worked very efficiently (99% yield after 2 h, 0.5 mol % of Pd) at room temperature (Table 5, entry 8). At this temperature, reducing the catalyst loading to 0.05 mol % of Pd (Table 5, entry 9), longer reaction times were necessary to completion. It was found that under these conditions the reaction proceeded sluggishly in the absence of oxygen (compare entries 9 and 10). However, the presence of external oxidants such as iodine[25] did not result in any significant improvement in rate or yield (compare entries 8 and 11). Other oxidants such as chloroacetone[23] seriously inhibited the reaction (Ta-

ble 5, entry 12). Therefore, oxime-derived palladacycle 8a is a competent promoter of the palladium-catalyzed homocoupling reaction of terminal alkynes at room temperature achieving turnover numbers of up to 1000.

Conclusion
In summary, we have shown that the phosphane-free oxime-derived palladacycle 8a, is an efficient and versatile pre-catalyst for the amine- and copper-free Sonogashira-type reaction of aryl iodides and aryl- and vinyl bromides with a variety of terminal acetylenes. The catalytic system has also been successfully applied to the cross-coupling of aryl iodides with alkynylsilanes. Tuning the reaction conditions, it is possible to control the reaction outcome to obtain either the diarylated alkynes (Methods A and B) or the silylated monoarylated alkynes (Method C). Complex 8a also catalyzes very efficiently, even at room temperature, the synthesis of conjugated diynes through the homocoupling of terminal alkynes using copper iodide as co-catalyst. Consequently, we have demonstrated that oxime-derived palladacycles are extremely active pre-catalysts for C(sp2)-C(sp) and C(sp)-C(sp) reaction couplings under air and very low loading conditions employing reagentgrade chemicals. Further studies on the applicability of these systems in other organic transformations are currently under investigation in our group.
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Scheme 5.
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Diego A. Alonso et al.

13 C NMR: d 11.3, 18.6, 91.8, 105.8, 122.0, 128.5, 133.2, 134.3; MS: m/z (rel. int.) 294 (M 2, 3), 292 (M, 8), 251 (31), 249 (M 43, 78), 223 (9), 221 (27), 209 (14), 207 (38), 195 (25), 193 (69), 181 (36), 179 (100), 165 (21), 163 (27), 139 (14), 97 (18), 63 (17); HRMS: calcd. for C17H25ClSi: 292.1414; found: 292.1429. 3-(4-Chlorophenyl)-1,1-dimethylprop-2-yn-1-ol (9d):[36] Rf: 0.12 (hexane/EtOAc, 9/1); mp 55 57 8C (toluene); IR (KBr): n 3725 3026 cm1 (OH); 1H NMR: d 1.61 (s, 6H, 2 CH3), 2.35 (s, 1H, OH), 7.25 7.35 (m, 4H, ArH); 13C NMR: d 31.3, 65.5, 81.0, 94.7, 121.2, 128.5, 132.8, 134.2; MS: m/z (rel. int.) 196 (M 2, 7), 194 (M, 21), 181 (31), 179 (M 15, 100), 159 (12), 136 (28), 116 (13), 115 (24), 101 (12), 75 (12). 3-(4-Chlorophenyl)prop-2-yn-1-ol (9e):[37] mp 76 78 8C (Lit. 78.5 79 0C); IR (KBr): n 3617 2979, 2241 cm1; 1 H NMR: d 1.82 (s, 1H, OH), 4.49 (s, 2H, CH2), 7.28, 7.36 (2d, 4H, J 8.64 Hz, ArH); 13C NMR: d 51.6, 84.6, 88.1, 121.0, 128.7, 132.9, 134.6; MS: m/z (rel. int.) 168 (M 2, 17), 167 (M 1, 14), 166 (M, 51), 165 (27), 149 (20), 138 (16), 137 (18), 136 (12), 132 (10), 131 (100), 114 (13), 113 (10), 103 (74), 102 (38), 101 (40), 77 (23), 75 (26), 74 (14), 63 (14), 51 (24). 3-(4-Chlorophenyl)prop-2-ynyl acetate (9e): Rf: 0.22 (hexane/EtOAc, 9/1); oil; IR (CH2Cl2): n 3086, 2237, 1748, 1223 cm1; 1H NMR: d 2.13 (s, 3H, CH3), 4.89 (s, 2H, CH2), 7.29, 7.38 (2d, 4H, J 8.51 Hz, ArH); 13C NMR: d 20.8, 52.7, 83.9, 85.3, 120.6, 128.7, 133.1, 134.9, 170.3; MS: m/z (rel. int.) 208 (M, 10), 193 (19), 151 (17), 150 (36), 149 (53), 148 (100), 145 (13), 137 (17), 131 (35), 114 (21), 113 (45), 102 (11), 101 (15), 75 (11), 63 (12); HRMS: calcd. for C11H9ClO2: 208.0291; found: 208.0273. 1-(1-Naphthyl)-2-phenylacetylene (9f):[19] Rf: 0.22 (hexane); oil; IR (film): n 3057, 2211 cm1; 1H NMR: d 7.37 7.77 (m, 11H, ArH), 8.44 (d, 1H, J 8.22 Hz, ArH); 13C NMR: d 87.5, 94.3, 120.9, 123.4, 125.3, 126.2, 126.4, 126.8, 128.3, 128.36, 128.42, 128.7, 130.3, 131.6, 133.2, 133.3; MS: m/z (rel. int.) 229 (M 1, 20), 228 (M, 100), 227 (M 1, 18), 226 (M 2, 40), 114 (16), 113 (18). 1-(4-Methoxyphenyl)-2-phenylacetylene (9 g):[5] Rf: 0.15 (hexane); mp 51 53 0C (Lit. 52 54 0C); IR (KBr): n 3053, 2216, 1246, 1028 cm1; 1H NMR: d 3.81 (s, 3H, CH3), 6.87 (d, 2H, J 8.52 Hz, ArH), 7.32 (m, 3H, ArH), 7.45 7.52 (m, 4H, ArH); 13C NMR: d 55.3, 88.0, 89.3, 114.0, 115.3, 123.6, 127.9, 128.3, 131.4, 133.0, 159.6; MS: m/z (rel. int.) 209 (M 1, 16), 208 (M, 100), 193 (53), 165 (53), 164 (19), 163 (15), 139 (16). 1-(4-Methoxyphenyl)-2-(triisopropylsilyl)acetylene (9 h):[38] Rf: 0.18 (hexane); oil; IR (film): n 3038, 3001, 2154, 1249, 1036 cm1; 1H NMR: d 1.12 [s, 21H, 3 CH(CH3)2], 3.80 (s, 3H, OCH3), 6.81, 7.41 (2d, 4H, J 8.45 Hz, ArH); 13 C NMR: d 11.4, 18.7, 55.3, 88.6, 107.1, 113.8, 115.8, 133.5, 159.6; MS: m/z (rel. int.) 288 (M, 23), 246 (22), 245 (100), 217 (24), 203 (47), 189 (53), 176 (13), 175 (79), 161 (11), 159 (14), 135 (10), 94 (19). 2-Phenylethynyl-N-acetylaniline (9j):[39] mp 120 122 0C (Lit. 119 121 0C); IR (KBr): n 3305, 1661, 1532 cm1; 1 H NMR: d 2.24 (s, 3H, CH3), 7.07 (t, 1H, J 7.55 Hz, ArH), 7.32 7.40 (m, 4H, ArH), 7.48 7.55 (m, 3H, ArH), 7.97 (s, 1H, NH), 8.41 (d, 1H, J 8.22 Hz, ArH); 13C NMR: d 24.9, 84.3, 96.4, 111.8, 119.3, 122.3, 123.4, 128.6, 128.9, 129.7, 131.5, 131.6, 138.9, 168.1; MS: m/z (rel. int.) 235 (M, 40), 194 (16), 193 (100), 192 (16), 165 (34), 90 (13), 89 (11). 1,2-Bis(1-octynyl)benzene (9k):[40] Rf: 0.17 (hexane); oil; IR (film): n 2228 cm1; 1H NMR: d 0.93 (t, 6H, J 6.87 Hz, 2 CH3), 1.35 1.71 (m, 16H, 8 CH2), 2.49 (t, 4H, J

Experimental Section
General
The reagents and solvents were obtained from commercial sources and were generally used without further purification. Palladacycle 8a can be purchased from MEDALCHEMY S. L. Gas chromatographic analyses were performed on an HP-5890 instrument equipped with a WCOT HP-1 fused silica capillary column using decane as internal standard. 1H NMR spectra were recorded on a Bruker AC-300 MHz spectrometer. Chemical shifts are reported in ppm using tetramethylsilane (TMS, 0.00 ppm) as internal standard. 13C NMR spectra were recorded at 75 MHz with CDCl3 as the internal reference. The catalysts were weighed out in an electronic microscale (Sartorius, XM1000P) with a precision of 1 mg. IR data were collected on a Nicolet Impact 400D of FT. Solid products were recrystallized in hexane/EtOAc unless otherwise stated, and melting points were not corrected. When mentioned, the reactions were set up with the aid of carousel reaction equipment equipped with gas-tight threaded caps with a valve, cooling reflux head system, and digital temperature controller. Compound 9b, reported in Table 2 (entry 2), has been previously reported[32] and was characterized by comparison of the GLC/MS and 1H NMR spectra; the purity was confirmed by GLC analysis. Compounds 9n,[31a] 9o[31a] and 9p[33] (Table 3, entries 5, 6 and 7, respectively) and compounds 12a,[34] 11c[35] and 12c[34] (Table 4), have been previously reported and were characterized by comparison of their GLC/MS and 1H NMR spectra; their purities were confirmed by GLC analyses.

Typical Procedure for Sonogashira-type Coupling of Aryl Iodides and Bromides with 1-Alkynes
A reaction tube of the carousel reaction equipment, was charged with 2-iodotoluene (65 mL, 0.5 mmol), decane (97 mL, 0.5 mmol), phenylacetylene (67 mL, 0.6 mmol), tetrabutylammonium acetate (171 mg, 0.55 mmol), 8a (0.204 mg, 0.00025 mmol, 0.1 mol % Pd) and NMP (2 mL). The mixture was stirred at 110 8C in air and the reaction progress was analyzed by GLC. The crude reaction mixture was extracted with water and EtOAc (3 15 mL). The organic phases were dried, evaporated (15 mm Hg) and the resulting crude material was purified by flash chromatography (hexane) affording pure 1-(2-methylphenyl)-2-phenylacetylene (9i);[5] yield: 76.3 mg (80%); Rf: 0.44 (hexane); oil; IR (film): n 3059, 3021, 2215 cm1; 1H NMR: d 2.51 (s, 3H, CH3), 7.12 7.23 (m, 3H, ArH), 7.31 7.34 (m, 3H, ArH), 7.48 7.55 (m, 3H, ArH); 13 C NMR: d 20.7, 88.3, 93.3, 123.0, 123.5, 125.6, 128.1, 128.3, 129.4, 131.5, 131.8, 140.1; MS: m/z (rel. int.) 193 (M 1, 15), 192 (M, 100), 191 (M 1, 92), 190 (18), 189 (34), 165 (28), 115 (13). 1-(4-Chlorophenyl)-2-phenylacetylene (9a):[10] mp 81 0C; IR (KBr): n 3048 cm1; 1H NMR: d 7.32 7.37 (m, 5H, ArH), 7.45 7.55 (m, 4H, ArH); 13C NMR: d 88.3, 90.3, 121.8, 123.0, 128.4, 128.5, 128.7, 131.6, 132.8, 134.3; MS: m/z (rel. int.) 214 (M 2, 32), 213 (M 1, 16), 212 (M, 100), 176 (41), 151 (15), 150 (11), 106 (10), 88 (11). 2-(4-Chlorophenyl)-1-(triisopropylsilyl)acetylene (9c): Rf: 0.65 (hexane); oil; IR (film): n 2157 cm1; 1H NMR: d 1.12 [m, 21H, 3 CH(CH3)2], 7.26, 7.39 (2d, 4H, J 8.52 Hz, ArH);
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C(sp2)-C(sp) and C(sp)-C(sp) Coupling Reactions 7.00 Hz, 2 CCH2), 7.18 7.21 (m, 2H, ArH), 7.38 7.41 (m, 2H, ArH); 13C NMR: d 14.1, 19.7, 22.6, 28.6, 28.8, 31.4, 79.5, 94.1, 126.3, 127.1, 131.8; MS: m/z (rel. int.) 294 (M, 29), 195 (17), 182 (13), 181 (68), 179 (21), 178 (23), 169 (28), 168 (18), 167 (90), 166 (35), 165 (70), 156 (12), 155 (55), 154 (25), 153 (48), 152 (62), 151 (20), 142 (24), 141 (100), 139 (13), 129 (30), 128 (29), 115 (18), 97 (11), 55 (48). 1-Bromo-2-(oct-1-ynyl)benzene (9k): Rf: 0.40 (hexane); oil; IR (film): n 2232 cm1; 1H NMR: d 0.91 (t, 3H, J 6.53 Hz, CH3), 1.24 1.68 (m, 8H, 4 CH2), 2.46 (t, 2H, J 6.86 Hz, CCH2), 7.10 (dt, 1H, J 7.82, 1.65 Hz, ArH), 7.22 (dt, 1H, J 7.55, 0.96 Hz, ArH), 7.42 (dd, 1H, J 7.68, 1.65 Hz, ArH), 7.55 (dd, 1H, J 7.96, 0.96 Hz, ArH); 13C NMR: d 14.1, 19.6, 22.57, 28.3, 28.5, 31.3, 79.3, 95.6, 125.4, 126.1, 126.8, 128.6, 132.2, 133.2; MS: m/z (rel. int.) 266 (M 2, 14), 264 (M, 12), 223 (19), 221 (18), 195 (27), 193 (20), 182 (20), 180 (15), 171 (22), 169 (22), 156 (40), 155 (11), 143 (26), 142 (87), 141 (45), 130 (16), 129 (81), 128 (64), 127 (23), 126 (10), 117 (16), 116 (100), 115 (77), 114 (63), 113 (25), 102 (12), 101 (12), 95 (40), 91 (12), 88 (20), 87 (10), 82 (10), 77 (10), 75 (13), 67 (15), 63 (16), 55 (11); HRMS: calcd. for C14H17Br: 264.0514; found: 264.0513. 1-Phenyl-2-(trifluoromethylphenyl)acetylene (9 l):[41] mp 103 0C; IR (KBr): n 2218 cm1; 1H NMR: d 7.34 7.36 (m, 3H, ArH), 7.53 7.60 (m, 6H, ArH); 13C NMR: d 88.0, 91.8, 122.5, 123.9 (J 270.5 Hz), 125.3 (J 14.6 Hz), 127.1, 128.4, 128.8, 129.9 (J 31.5 Hz), 131.7, 131.8; MS: m/z (rel. int.) 247 (M 1, 20), 246 (M, 100), 196 (12), 176 (14), 98 (31), 85 (12), 75 (13). 1-(Oct-1-ynyl)naphthalene (9 m): Rf: 0.38 (hexane); oil; IR (film): n 3058, 2955, 2930, 2857, 2224 cm1; 1H NMR: d 0.92 (t, 1H, J 6.87 Hz, CH3), 1.34 1.74 (m, 8H, 4 CH2), 2.55 (t, 2H, J 7.07 Hz,  CCH2), 7.38 (t, 1H, J 7.38 Hz, ArH), 7.45 7.57 (m, 2H, ArH), 7.61 (d, 1H, J 6.3 Hz, ArH), 7.75 (d, 1H, J 8.22 Hz, ArH), 7.81 (d, 1H, J 7.53 Hz, ArH), 8.25 (d, 1H, J 8.04 Hz, ArH); 13C NMR: d 14.1, 19.7, 22.6, 28.7, 28.9, 31.4, 78.6, 95.6, 121.8, 125.2, 126.2, 126.3, 126.4, 127.8, 128.2, 129.9, 133.2, 133.5; MS: m/z (rel. int.) 236 (M, 35), 207 (12), 193 (22), 179 (28), 178 (28), 167 (60), 166 (24), 165 (100), 164 (25), 163 (21), 153 (13), 152 (27), 141 (10); HRMS: calcd. for C18H20: 236.1565; found: 236.1550. 1-(4-Methylphenyl)-2-(triisopropylsilyl)acetylene (9q): Rf: 0.28 (hexane); oil; IR (film): n 3081, 3049, 3028, 2155 cm1; 1 H NMR: d 1.12 [m, 21H, 3 CH(CH3)2], 2.33 (s, 3H, ArCH3), 7.09, 7.37 (2d, 4H, J 7.92 Hz, ArH); 13C NMR: d 11.3, 18.7, 21.5, 89.5, 107.3, 120.5, 128.9, 131.9, 138.4; MS: m/z (rel. int.) 272 (M, 7), 230 (16), 229 (70), 201 (22), 187 (41), 174 (11), 173 (60), 160 (16), 159 (100), 145 (16), 143 (29), 119 (19), 86 (20); HRMS: calcd. for C18H28Si: 272.1960; found: 272.1966. 2-[4-(Oct-1-ynyl)phenyl]-1,3-dioxolane (9r): Rf: 0.31 (hexane/EtOAc, 9/1); oil; IR (film): n 2226 cm1; 1H NMR: d 0.90 (m, 3H, CH3), 1.26 1.65 (m, 8H, 4 CH2), 2.40 (t, 2H, J 7.07 Hz, CCH2), 4.00 4.14 (m, 4H, OCH2CH2O), 5.79 (s, 1H, OCHO), 7.38, 7.51 (2d, 4H, J 8.37 Hz, ArH); 13C NMR: d 14.0, 19.4, 22.5, 28.6, 28.7, 31.3, 65.3, 80.3, 91.1, 103.4, 125.0, 126.3, 131.5, 137.0; MS: m/z (rel. int.) 258 (M, 53), 257 (M 1, 92), 213 (18), 187 (21), 157 (18), 144 (25), 143 (62), 142 (14), 141 (18), 131 (13), 130 (23), 129 (53), 128 (52), 127 (19), 117 (42), 116 (25), 115 (100), 104 (15), 102 (12), 91 (20), 73 (94); HRMS: calcd. for C17H22O2: 258.1620; found: 258.1587. 1,4-Di(oct-1-ynyl)benzene (9 s):[42] Rf: 0.36 (hexane); oil; IR (film): n 2228 cm1; 1H NMR: d 0.90 (t, 6H, J 6.86 Hz,
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2 CH3), 1.29 1.64 (m, 16H, 8 CH2), 2.40 (t, 4H, J 7.07 Hz, 2 CCH2), 7.29 (s, 4H, ArH); 13C NMR: d 14.0, 19.5, 22.6, 28.6, 28.7, 31.4, 80.4, 91.9, 123.2, 131.3; MS: m/z (rel. int.) 295 (M 1, 15), 294 (M, 65), 251 (22), 225 (31), 223 (22), 183 (11), 181 (19), 179 (20), 178 (21), 169 (24), 168 (12), 167 (45), 166 (30), 165 (72), 157 (11), 156 (13), 155 (68), 154 (20), 153 (51), 152 (82), 151 (22), 143 (23), 142 (21), 141 (100), 139 (47), 130 (11), 129 (80), 128 (34), 127 (11), 126 (11), 115 (33), 109 (16), 91 (11), 79 (12), 67 (24), 55 (36). 1-Bromo-4-(oct-1-ynyl)benzene (9 s): Rf: 0.18 (hexane); oil; IR (CH2Cl2): n 2204 cm1; 1H NMR: d 0.89 (m, 3H, CH3), 1.30 1.68 (m, 8H, 4 CH2), 2.38 (t, 2H, J 7.07 Hz, CCH2), 7.24, 7.40 (2d, 4H, J 8.51 Hz, ArH); MS: m/z (rel. int.) 266 (M 2, 17), 264 (M, 17), 223 (15), 221 (15), 197 (13), 195 (40), 193 (27), 182 (16), 180 (10), 171 (14), 169 (15), 156 (31), 143 (29), 142 (86), 141 (38), 130 (11), 129 (66), 128 (55), 127 (21), 117 (14), 116 (100), 115 (56), 114 (48), 113 (23), 102 (10), 101 (11), 95 (10), 88 (17), 63 (15); HRMS: calcd. for C14H17Br: 264.0514; found: 264.0535. 1,4-Bis(2-phenyl-1-ethynyl)benzene (9 t):[43] Rf: 0.20 (hexane); mp 177 179 0C (Lit. 178 180 0C); IR (KBr): n 3048, 1595, 1516 cm1; 1H NMR: d 7.34 7.36 (m, 6H, ArH), 7.51 7.55 (m, 8H, ArH); 13C NMR: d 89.1, 91.2, 123.0, 123.1, 128.38, 128.45, 131.5, 131.6; MS: m/z (rel. int.) 279 (M 1, 26), 278 (M, 100), 276 (17), 139 (19). 1,3,5-Tri(oct-1-ynyl)benzene (9u): Rf: 0.29 (hexane); oil; IR (film): n 2229, 2200 cm1; 1H NMR: d 0.902 (t, 9H, J 6.66 Hz, 3 CH3), 1.31 1.62 (m, 24H, 12 CH2), 2.37 (t, 6H, J 6.93 Hz, 3 CCH2), 7.30 (s, 3H, ArH); 13C NMR: d 14.1, 19.3, 22.6, 28.56, 28.61, 31.4, 79.4, 91.2, 124.3, 133.5; MS: m/z (rel. int.) 403 (M 1, 11), 402 (M, 32), 359 (13), 333 (22), 219 (11), 216 (11), 215 (13), 209 (16), 208 (18), 207 (100), 205 (22), 203 (21), 202 (23), 193 (23), 191 (29), 190 (15), 189 (25), 179 (38), 178 (22), n167 (19), 165 (30), 153 (11), 152 (12), 133 (11), 109 (23), 96 (21), 95 (20), 81 (12), 79 (15), 73 (10), 69 (12), 67 (33), 55 (45); HRMS: calcd. for C30H42: 402.3287; found: 402.3278. 1-Bromo-3,5-di(oct-1-ynyl)benzene (9u): oil; MS: m/z (rel. int.) 374 (M 2, 22), 372 (M, 21), 331 (12), 224 (20), 209 (21), 208 (28), 207 (99), 195 (19), 194 (17), 193 (22), 192 (13), 191 (18), 183 (10), 182 (33), 181 (34), 180 (27), 179 (49), 178 (49), 177 (12), 169 (15), 168 (22), 167 (62), 166 (45), 165 (100), 164 (19), 163 (21), 156 (16), 155 (54), 154 (22), 153 (52), 152 (60), 151 (34), 150 (30), 142 (20), 141 (48), 139 (23), 133 (12), 129 (16), 128 (27), 115 (14), 109 (14), 96 (19), 95 (48), 93 (16), 91 (11), 81 (13), 79 (26), 69 (14), 37 (30), 55 (39); HRMS: calcd. for C22H29Br: 372.1453; found: 372.1458. 1,3-Dibromo-5-(oct-1-ynyl)benzene (9u): oil; IR (CH2Cl2): n 2227 cm1; 1H NMR: d 0.91 (t, 3H, J 6.86 Hz, CH3), 1.24 1.61 (m, 8H, 4 CH2), 2.39 (t, 2H, J 6.99 Hz, CH2), 7.46 (d, 2H, J 1.77 Hz, ArH), 7.56 (d, 2H, J 1.77 Hz, ArH); MS: m/z (rel. int.) 346 (M 4, 10), 344 (M 2, 20), 342 (M, 10), 331 (15), 275 (10), 273 (18), 260 (15), 249 (10), 236 (14), 234 (13), 222 (20), 221 (10), 220 (17), 196 (18), 195 (15), 194 (28), 193 (15), 155 (24), 142 (26), 141 (50), 129 (16), 128 (100), 127 (25), 126 (23), 115 (32), 114 (23), 113 (53), 95 (33), 87 (13), 82 (13), 69 (29), 67 (24), 55 (15); HRMS calcd. for C14H16Br2: 341.9619; found: 341.9660. 2-(Oct-1-ynyl)thiophene (9v):[44] Rf: 0.48 (hexane); oil; IR (film): n 2225 cm1; 1H NMR: d 0.90 (t, 3H, J 6.80 Hz, CH3), 1.29 1.62 (m, 8H, 4 CH2), 2.41 (t, 3H, J 7.07 Hz,  CCH2), 6.93 (dd, 1H, J 5.07, 3.69 Hz, ArH), 7.11 (d, 1H, J
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3.45 Hz, ArH), 7.16 (d, 1H, J 5.22 Hz, ArH); 13C NMR: d 14.0, 19.7, 22.5, 28.5, 28.6, 31.3, 73.6, 94.6, 124.3, 125.8, 126.7, 130.8; MS: m/z (rel. int.) 192 (M, 32), 163 (22), 150 (18), 149 (36), 136 (25), 135 (42), 134 (21), 124 (13), 123 (100), 122 (14), 121 (83), 116 (10), 115 (34), 110 (15), 108 (19), 97 (28), 91 (13), 79 (13), 77 (28), 69 (11), 63 (11). Triisopropyl[(E)-4-phenyl-3-buten-1-ynyl]silane (10):[45] oil; IR (film): n 3081, 3061, 3029, 2165, 2118 cm1; 1 H NMR: d 1.11 [m, 21H, 3 CH(CH3)2], 6.21 and 6.99 (2d, 2H, J 16.47 Hz, CHCH), 7.25 7.39 (m, 5H, ArH); 13 C NMR: d 11.3, 18.6, 93.3, 106.2, 108.4, 126.2, 128.6, 128.7, 136.2, 142.0; MS: m/z (rel. int.) 284 (M, 19), 242 (24), 241 (M 43, 100), 213 (18), 199 (30), 186 (11), 185 (61), 183 (26), 172 (16), 171 (88), 169 (19), 167 (11), 157 (19), 155 (34), 145 (31), 131 (14), 129 (24), 105 (10), 92 (29), 59 (36).

Diego A. Alonso et al. 132.7, 133.4; MS: m/z (rel. int.) 180 (M 2, 22), 178 (M, 54), 163 (10), 151 (36), 150 (12), 149 (100), 143 (39), 142 (18), 141 (14), 136 (14), 128 (72), 127 (32), 115 (25), 114 (26), 113 (21), 99 (18), 98 (12), 75 (11), 63 (16); HRMS: calcd. for C11H11Cl: 178.0549; found: 178.0539.

Typical Procedure for Sila-Sonogashira Coupling of Aryl Iodides and Bromides to Afford Silylated Alkynes
Method C: A reaction tube of the carousel reaction equipment was charged with 1-iodonaphthalene (295 mL, 2 mmol), decane (390 mL, 2 mmol), bis(trimethylsilyl) acetylene (542 mL, 2.4 mmol) or trimethylsilylacetylene (340 mL, 2.4 mmol), tetrabutylammonium bromide (129 mg, 0.4 mmol), pyrrolidine (177 mL, 2.1 mmol), catalyst 8a (4.079 mg, 0.005 mmol, 0.5 mol % Pd) and NMP (4 mL). The mixture was stirred at 110 0C in air and the reaction progress was analyzed by GLC. The crude reaction mixture was extracted with water and EtOAc (3 15 mL). The organic phases were dried, evaporated (15 mm Hg) and the resulting crude was purified by flash chromatography (hexane/EtOAc) affording the corresponding trimethyl[2-(1-naphthyl)-1-ethynyl]silane (12b);[47] oil; IR (film): n 2147 cm1; 1H NMR: d 0.34 (s, 9H, 3 CH3), 7.37 7.84 (m, 6H, ArH), 8.34 (d, 1H, J 7.89 Hz, ArH); 13 C NMR: d 99.4, 103.1, 120.7, 125.1, 126.2, 126.3, 126.8, 128.2, 129.0, 130.8, 133.1; MS: m/z (rel. int.) 224 (M, 36), 210 (20), 209 (100), 179 (10), 165 (23), 104 (11).

Typical Procedure for Sila-Sonogashira Coupling of Aryl Iodides and Bromides to Afford Diarylated Alkynes
Method A: A 25-mL round-bottom flask was charged with 1iodonaphthalene (295 mL, 2 mmol), decane (194 mL, 1 mmol), bis(trimethylsilyl)acetylene (345 mL, 1.5 mmol) or trimethylsilylacetylene (340 mL, 2.4 mmol), CuI (19.4 mg, 0.1 mmol), 8a (4.079 mg, 0.005 mmol, 0.5 mol % Pd) and pyrrolidine (6 mL). The mixture was stirred at 90 0C in air and the reaction progress was analyzed by GLC. The crude reaction mixture was extracted with water and EtOAc (3 15 mL). The organic phases were dried, evaporated (15 mm Hg) and the resulting crude was purified by flash chromatography (hexane/EtOAc) affording the corresponding 1,2-di(1-naphthyl)acetylene (11b);[46] yield: 756.3 mg (54%); Rf: 0.23 (hexane/EtOAc, 99/ 1); mp 125 0C (Lit. 127 129 0C); IR (KBr): n 3052, 3044 cm1; 1H NMR: d 7.48 7.67 (m, 6H, ArH), 7.87 7.91 (m, 6H, ArH), 8.57 (d, 2H, J 8.3 Hz, ArH); 13C NMR: d 92.4, 121.1, 125.3, 126.3, 126.5, 126.9, 128.4, 128.9, 130.6, 133.3; MS: m/z (rel. int.) 279 (M 1, 24), 278 (M, 100), 277 (M 1, 23), 276 (M-2, 47), 139 (30), 138 (50), 137 (26), 125 (20). Method B: A reaction tube of the carousel reaction equipment was charged with 1-iodonaphthalene (148 mL, 1 mmol), decane (194 mL, 1 mmol), bis(trimethylsilyl)acetylene (136 mL, 0.6 mmol), pyrrolidine (253 mL, 3 mmol), CuI (9.7 mg, 0.05 mmol), 8a (1.020 mg, 0.00125 mmol, 0.25 mol % Pd) and NMP (2 mL). The mixture was stirred at 110 0C in air and the reaction progress was analyzed by GLC. The crude reaction mixture was extracted with water and EtOAc (3 15 mL). The organic phases were dried, evaporated (15 mm Hg) and the resulting crude was purified by flash chromatography (hexane/EtOAc) affording the corresponding 1,2-di(1-naphthyl)acetylene (11b). 1,2-Bis(4-chlorophenyl)acetylene (11a):[41] Rf: 0.52 (hexane/ EtOAc, 99/1); mp 176 0C (Lit. 174 176 0C); IR (KBr): n 3078, 831 cm1; 1H NMR: d 7.32 (d, 4H, J 8.3 Hz, ArH), 7.45 (d, 4H, J 8.3 Hz, ArH); 13C NMR: d 89.2, 121.4, 128.7, 132.8, 134.5; MS: m/z (rel. int.) 248 (M 2, 50), 246 (M, 100), 176 (47), 123 (22), 99 (10), 88 (19), 75 (17). 1-Chloro-4-(pent-1-ynyl)benzene (9w): Rf: 0.52 (hexane); oil; IR (film): n 3054, 3035, 2237 cm1; 1H NMR: d 1.04 (t, 3H, J 7.41 Hz, CH3), 1.51 1.68 (m, 2H, CH3CH2), 2.37 (t, 2H, J 6.99 Hz,  CCH2), 7.24, 7.32 (2d, 4H, J 8.39 Hz, ArH); 13C NMR: d 13.5, 21.4, 22.1, 79.6, 91.3, 122.6, 128.4,
1156 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Typical Procedure for the Homocoupling Reaction of Terminal Alkynes

A reaction tube of the carousel reaction equipment was charged with 1-octyne (152 mL, 1 mmol), decane (97 mL, 0.5 mmol), pyrrolidine (93 mL, 1.1 mmol), CuI (9.7 mg, 0.05 mmol), 8a (0.204 mg, 0.00025 mmol, 0.05 mol % Pd) and NMP (2 mL). The mixture was stirred at the temperature indicated in Table 5 (110 0C or rt) in air and the reaction progress was analyzed by GLC. The crude reaction mixture was extracted with water and EtOAc (3 15 mL). The organic phases were dried, evaporated (15 mm Hg) and the resulting crude was purified by flash chromatography (hexane/EtOAc) affording the corresponding 7,9-hexadecadiyne (13a);[19] yield: 65 mg (60%); oil; IR (film): n 2956, 2931, 2871, 2859, 2233 cm1; 1H NMR: d 0.89 (t, 6H, J 6.8 Hz, 2 CH3), 1.22 1.56 (2 m, 16H, 8 CH2), 2.24 (t, 4H, J 7.0 Hz, 2  CCH2); 13C NMR: d 14.0, 19.2, 22.5, 28.3, 28.5, 31.3, 65.3, 77.3; MS: m/z (rel. int.) 189 (M 29, 3), 147 (5), 133 (9), 119 (16), 105 (29), 91 (58), 79 (41), 77 (25), 67 (47), 55 (40), 44 (34), 41 (100). 8,10-Octadecadiyne (13b):[48] Rf: 0.58 (hexane); oil; IR (film): n 2234 cm1; 1H NMR: d 0.87 (t, 6H, J 6.72 Hz, 2 CH3), 1.27 1.53 (m, 20H, 10 CH2), 2.23 (t, 4H, J 6.71 Hz, 2 CCH2); 13C NMR: d 14.0, 19.2, 22.6, 28.3, 28.75, 28.78, 31.7, 65.2, 77.5; MS: m/z (rel. int.) 246 (M, 0.1), 161 (12), 147 (20), 135 (14), 133 (36), 122 (11), 121 (30), 120 (13), 119 (51), 117 (18), 115 (12), 109 (19), 107 (38), 106 (13), 105 (60), 103 (12), 95 (28), 94 (15), 93 (48), 92 (21), 91 (100), 81 (51), 80 (14), 79 (60), 78 (28), 77 (33), 69 (16), 67 (56), 65 (16), 57 (10), 55 (49), 51 (11).
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C(sp2)-C(sp) and C(sp)-C(sp) Coupling Reactions

FULL PAPERS
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1,4-Diphenyl-1,3-butadiyne (13c):[19] Rf: 0.33 (hexane/ EtOAc, 99/1); mp 87 0C (Lit. 87 0C); IR (KBr): n 3047 cm1; 1 H NMR: d 7.33 7.36 (m, 6H, ArH), 7.52 7.55 (m, 4H, ArH); 13C NMR: d 73.9, 81.6, 124.8, 128.4, 129.2, 132.5; MS: m/z (rel. int.) 202 (M, 100), 200 (M 2, 25), 101 (15), 88 (9). 1,4-Bis(triisopropylsilyl)-1,3-butadiyne (13d):[49] mp 108 110 0C; IR (KBr): n 2061 cm1; 1H NMR: d 1.09 [s, 42H, 6 CH(CH3)2]; 13C NMR: d 11.3, 18.6, 81.5, 90.2; MS: m/z (rel. int.) 362 (M, 13), 321 (11), 320 (31), 319 (M-43, 100), 291 (18), 277 (17), 263 (14), 249 (24), 137 (12), 82 (27), 73 (12), 59 (13). 2,7-Dimethyl-3,5-octadiyne-2,7-diol (13e):[42] Rf: 0.83 (hexane/EtOAc, 3/2); mp 131 133 0C (Lit. 133 0C); IR (KBr): n 3664 2663, 2144 cm1; 1H NMR: d 1.53 (s, 12H, 4 CH3), 1.89 (s, 2H, CH2); 13C NMR: d 31.0, 65.6, 66.3, 84.0; MS: m/z (rel. int.) 166 (M, 4), 152 (11), 151 (100), 134 (13), 133 (85), 123 (52), 109 (24), 108 (15), 107 (15), 106 (19), 105 (80), 93 (35), 91 (33), 81 (10), 79 (30), 77 (47), 75 (11), 74 (11), 69 (33), 68 (12), 67 (19), 65 (27), 63 (26), 62 (11), 55 (27), 53 (22), 51 (24).

Acknowledgements
n This work has been supported by the Direccio General de n Investigacio of the Ministerio de Ciencia y Tecnologa (MCyT) (BQU2001 0724-CO2 01). D. A. A. thanks MCyT for a n contract under the program Ramo y Cajal. M. C. P. thanks Generalitat Valenciana for a predoctoral fellowship.

References and Notes

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