Fukuyama reduction

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The Fukuyama reduction is an organic reaction and an organic reduction in which a thioester is reduced to an aldehyde by a silyl hydride in presence of a catalytic amount of palladium. This reaction was invented in 1990 by Tohru Fukuyama.[1] In the original scope of the reaction the silyl hydride was triethylsilyl hydride and the catalyst palladium on carbon:

The Fukuyama reduction

Fukuyama reductions are used for the conversion of carboxylic acids (as thioester precursor) to aldehydes which is considered a difficult procedure because of the ease of secondary reduction to an alcohol.

Reaction mechanism[edit]

The basic reaction mechanism for this reaction takes place as a catalytic cycle:

R-C(O)-SR + Pd(0) → RC(O)-Pd(II)-SR
RC(O)-Pd(II)-SR + R3SiH → RC(O)-Pd(II)-H + R3Si-SR
RC(O)-Pd(II)-H → RC(O)-H + Pd(0)

Scope[edit]

In a variation of the Fukuyama reduction the core BODIPY molecule has been synthesized from the SMe-substituted derivative:[2][3]

BODIPY synthesis Arroyo 2009

In the related Fukuyama coupling the hydride is replaced by a carbon nucleophile.

References[edit]

  1. ^ Facile reduction of ethyl thiol esters to aldehydes: application to a total synthesis of (+)-neothramycin A methyl ether Tohru Fukuyama, Shao Cheng Lin, Leping Li J. Am. Chem. Soc., 1990, 112 (19), pp 7050–7051 doi:10.1021/ja00175a043
  2. ^ The Smallest and One of the Brightest. Efficient Preparation and Optical Description of the Parent Borondipyrromethene System. I. J. Arroyo, R. Hu, G. Merino, B. Z. Tang, E. Peña-Cabrera, J. Org. Chem. 2009, ASAP
  3. ^ Additional reagents CuTC, Pd(dba)2, tri(2-furyl)phosphine