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:
- Transmetallation:
- Reductive elimination:
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
- v
- t
- e
- A value
- Alpha effect
- Annulene
- Anomeric effect
- Antiaromaticity
- Aromatic ring current
- Aromaticity
- Baird's rule
- Baker–Nathan effect
- Baldwin's rules
- Bema Hapothle
- Beta-silicon effect
- Bicycloaromaticity
- Bredt's rule
- Bürgi–Dunitz angle
- Catalytic resonance theory
- Charge remote fragmentation
- Charge-transfer complex
- Clar's rule
- Conformational isomerism
- Conjugated system
- Conrotatory and disrotatory
- Curtin–Hammett principle
- Dynamic binding (chemistry)
- Edwards equation
- Effective molarity
- Electromeric effect
- Electron-rich
- Electron-withdrawing group
- Electronic effect
- Electrophile
- Evelyn effect
- Flippin–Lodge angle
- Free-energy relationship
- Grunwald–Winstein equation
- Hammett acidity function
- Hammett equation
- George S. Hammond
- Hammond's postulate
- Homoaromaticity
- Hückel's rule
- Hyperconjugation
- Inductive effect
- Kinetic isotope effect
- LFER solvent coefficients (data page)
- Marcus theory
- Markovnikov's rule
- Möbius aromaticity
- Möbius–Hückel concept
- More O'Ferrall–Jencks plot
- Negative hyperconjugation
- Neighbouring group participation
- 2-Norbornyl cation
- Nucleophile
- Kennedy J. P. Orton
- Passive binding
- Phosphaethynolate
- Polar effect
- Polyfluorene
- Ring strain
- Σ-aromaticity
- Spherical aromaticity
- Spiroaromaticity
- Steric effects
- Superaromaticity
- Swain–Lupton equation
- Taft equation
- Thorpe–Ingold effect
- Vinylogy
- Walsh diagram
- Woodward–Hoffmann rules
- Woodward's rules
- Y-aromaticity
- Yukawa–Tsuno equation
- Zaitsev's rule
- Σ-bishomoaromaticity