Sodium cyanoborohydride enones

Sodium cyanoborohydride (NaBHsCN) or tetrabutylammonium cyanoborohydride in acidic methanol or acidic HMPA reduces a,p-unsaturated aldehydes and ketones to the corresponding allylic alcohols. This system is limited to enones in which the double bond is not further conjugated, in which case the allylic hydrocarbon is formed in substantial amounts. Thus, reduction of chalcone gives mainly 1,3-di-phenylpropene (48%) as well as 26% of the allylic ether. Cyclic enones are also not good substrates, as competing 1,4-addition gives large fractions of saturated alcohols. ... 

Lhommet and co-workers synthesized (- )-436 by the route shown in Scheme 66 [422). Wittig-Homer reaction between the 2,5-rrans -disubstituted pyrrolidine aldehyde 509, made from (S)-pyroglutamic acid [423), and the protected keto-phosphonate 510 introduced all the skeletal carbon atoms of the target. Simultaneous hydrogenation and //-deprotection of enone 511 gave the aminoketone 512, which spontaneously formed the bicyclic enamine 513 in 98% yield when exposed to trifluoroacetic acid—apparently the first time that such an intermediate has actually been isolated en route to indolizidines. Reduction with sodium cyanoborohydride in acidic medium acid produced a diastereomeric mixture (92 8) of (- )-436 and (+ )-437. The former was isolated in 84% yield after chromatography on silica gel. The overall yield of this 15-step sequence was 8% based on (S)-pyroglutamic acid. 

Reduction of conjugated carbonyl compounds using stoichiometric amounts of the ammonium salt shows little advantage over the sodium salt in acidic methanol [11] with both reagents producing allylic alcohols (58-88% for acyclic compounds and 15-64% for cyclic compounds) by selective 1,2-reduction of the conjugated systems. Aldehydes, ketones and conjugated enones are also reduced by tetra-n-butylammonium cyanoborohydride in HMPA [11, 12], whereas haloalkanes and alkanesulphonic esters are cleaved reductively under similar conditions [13]. 

Sodium borohydride adsorbed on alumina is a new reagent combination for the reduction of aldehydes and ketones to alcohols in aprotic solvents such as ether. Cyanoborohydride anion, [BHsCN] , supported on an anion-exchange resin containing quaternary ammonium groups has been found in preliminary results to be a successful and convenient reagent for, inter alia, the reduction of enones to allylic alcohols. Ease of work-up and retention of cyanide by the resin are obvious advantages. Carbonyl compounds can also be reduced to alcohols by tributyltin hydride in a cyclohexane-silica gel slurry aldehydes are selectively reduced in the presence of ketones and products are obtained by simple elution from the silica. Adsorption, and consequent polarization, of the carbonyl group by the silica seems to be important in the mechanism of this mild, non-basic, process. 

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