Chemistry:Fukuyama reduction
| Fukuyama reduction | |
|---|---|
| Named after | Tohru Fukuyama |
| Reaction type | Organic redox reaction |
| Identifiers | |
| Organic Chemistry Portal | fukuyama-reduction |
| RSC ontology ID | RXNO:0000680 |
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 triethylsilane and the catalyst palladium on carbon:
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
The basic reaction mechanism for this reaction takes place as a catalytic cycle:
- Oxidative addition:
- [math]\ce{ {R-C(O)-SR} + Pd^0 -> RC(O)-Pd^{II}-SR }[/math]
- Transmetallation:
- [math]\ce{ {RC(O)-Pd^{II}-SR} + R3SiH -> {RC(O)-Pd^{II}-H} + R3Si-SR }[/math]
- Reductive elimination:
- [math]\ce{ RC(O)-Pd^{II}-H -> {RC(O)-H} + Pd^0 }[/math]
Scope
In a variation of the Fukuyama reduction the core BODIPY molecule has been synthesized from the SMe-substituted derivative:[2] Additional reagents are copper(I)-thiophene-2-carboxylate (CuTC), Pd(dba)2 and tri(2-furyl)phosphine
In the related Fukuyama coupling the hydride is replaced by a carbon nucleophile.
References
- ↑ 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
- ↑ 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
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