Table 4.3.

Typical reductions with selected hydride reagents

Hydride Applications Special Considerations

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