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4.6. Borane, Aluminum Hydride, and Derivatives

The document summarizes typical reductions using selected hydride reagents. It provides a table that lists common hydride reagents, their applications, and special considerations for each. The hydride reagents include LiAlH4, LiAlH(OMe)3, LiAlH(Ot-Bu)3, Red-Al, NaBH4, LiBH4, Zn(BH4)2, NaBH4•CeCl3, MBH(O2CR)3, LiBHEt3, MBH(sec-Bu)3, and NaBH3CN. The table describes what functional groups and compounds each reagent is generally used to reduce as well as any limitations or selectivity issues for each re

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Dr.Rajarshi Patel
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54 views

4.6. Borane, Aluminum Hydride, and Derivatives

The document summarizes typical reductions using selected hydride reagents. It provides a table that lists common hydride reagents, their applications, and special considerations for each. The hydride reagents include LiAlH4, LiAlH(OMe)3, LiAlH(Ot-Bu)3, Red-Al, NaBH4, LiBH4, Zn(BH4)2, NaBH4•CeCl3, MBH(O2CR)3, LiBHEt3, MBH(sec-Bu)3, and NaBH3CN. The table describes what functional groups and compounds each reagent is generally used to reduce as well as any limitations or selectivity issues for each re

Uploaded by

Dr.Rajarshi Patel
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Table 4.3.

Typical reductions with selected hydride reagents

Hydride Applications Special Considerations


LiAlH4 General. reduces most groups: aldehydes, ketones, Aromatic nitro reduced to diazo. Sulfonate esters
acids and acid derivatives, nitriles, aliphatic nitro, give mixtures of C–O and S–O cleavage. Conjugated
halides, propargyl alcohols. carbonyls often give mixtures of 1,2- and 1,4-reduction.
LiAlH(OMe)3 Milder than LiAlH4. Generally used for aldehydes, Esters are reduced more slowly than ketones or aldehydes.
ketones, and conversion of acid chlorides or esters Conjugated carbonyls give mostly 1,2-reduction. Amides
to aldehydes. and nitriles are reduced to aldehydes.
LiAlH(Ot-Bu)3 Mild and selective. Good for converting acid Esters are reduced more slowly than ketones or aldehydes.
derivatives to aldehydes. Conjugated carbonyls give mostly 1,2-reduction. Amides
and nitriles are reduced to aldehydes.
Red-Al Similar to LiAlH4. Good for carboxylic acids. Conjugate carbonyls give 1,2-reduction (1,4- when Cu+ is
Nitriles can be converted to aldehydes and added). Soluble in oranic solvents, so excellent for reverse
aromatic aldehydes to methyl aryls. addition experiments.
NaBH4 General but mild. Good for ketones, aldehydes, Esters and most acid derivatives reduce slowly, or not at
acid chlorides, imines, iminium salts. all. Conjugated carbonyls give mostly 1,2-reduction, but
1,4-reduction is common. Halides are not reduced very
well, but epoxides reduce very slowly
LiBH4 Good for esters. Stronger than NaBH4–, but Similar to NaBH4, except for esters.
less selective.
Zn(BH4)2 Generally similar to NaBH4, but shows higher Similar to NaBH4.
diastereoselectivity.
NaBH4•CeCl3 Gives primarily 1,2-reduction with conjugated Similar to NaBH4.
carbonyls.
MBH(O2CR)3 Good for imines and enamines. Reducing power is dependent on solvent and the nature
of the R group in the RCOOH precursor. Alkylation can
occur with amines, and hydroboration can occur with
alkenes.
LiBHEt3 Strong reducing agent. Good for halides Similar to LiAlH4
(Super Hydride) (SN2-type reductions), halides, and sulfonate
esters (C–O cleavage).
MBH(sec-Bu)3 Used primarily with aldehydes and ketones Similar to LiAlH4
(Selectride) when higher diastereoselectivity is required.
NaBH3CN Excellent for reduction of halides at neutral Generally unreactive with most groups at neutral pH.
pH, and alcohols if a Lewis acid is added. Reduces aldehydes and ketones at pH 4 and lower. Acid
derivatives are generally unreactive.

4.6. BORANE, ALUMINUM HYDRIDE, AND DERIVATIVES


4.6.A. Borane
Brown and Schlesinger first reported the preparation and use of diborane as a reducing agent
in 1939.203 This finding began the exploration of hydrides and boranes as reducing agents.
Borane reagents are discussed after hydrides only because hydride reagents are now used
more often, but borane and its derivatives remain the reagent of choice for many applications.
Diborane can be generated by reaction of BF3•OEt2 with LiH204 or by reaction of NaBH4 and
BF3 (sec. 5.2.A).205

203. Brown, H.C.; Schlesinger, H.I.; Burg, A.B. J. Am. Chem. Soc. 1939, 61, 673.
204. Schlesinger, H.I.; Brown, H.C.; Hoekstra, H.R.; Rapp, L.R. J. Am. Chem. Soc. 1953, 75, 199.
205. Zweifel, G.; Brown, H.C. Org. React. 1963, 13, 1.

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