Herein we review recent advances in the asymmetric reduction of ketones by biocatalysts. Included are discussions on recent developments in methodologies to control enantioselectivities of catalytic reactions, and examples of practical applications that reduce various types of ketones are also shown.

Recent developments in asymmetric reduction of ketones with biocatalysts

Enantioselective enzymatic desymmetrizations in organic synthesis.

https://www.scripps.edu/barbas/pdf/Bui00TetLt.pdf

A proline-catalyzed asymmetric Robinson annulation reaction

Dehydrogenases and transaminases in asymmetric synthesis.

Update 1 of: Enantioselective Enzymatic Desymmetrizations in Organic Synthesis Eduardo García-Urdiales, Ignacio Alfonso, and Vicente Gotor* Departamento de Química Org anica e Inorg anica, Facultad de Química, Universidad de Oviedo, Juli an Clavería, 8, 33006 Oviedo, Spain, and Departamento de Química Biol ogica y Modelizaci on Molecular, Instituto de Química Avanzada de Catalu~na (IQAC, CSIC), Jordi Girona, 18-26, 08034, Barcelona, Spain This is a Chemical Reviews Perennial Review. The root paper of this title was published in Chem. Rev. 2005, 105 (1), 313 354, DOI: 10.1021/cr040640a; Published (Web) December 17, 2004. Updates to this text appear in red type.

Update 1 of: Enantioselective enzymatic desymmetrizations in organic synthesis.

Both enantiomers of Wieland-Miescher ketone [3,4,8, 8a-tetrahydro-8a-methyl-1,6(2H,7H)-naphthalenedione], in a highly enantiomerically enriched form, became readily available by a newly developed kinetic resolution with yeast-mediated reduction. From a screening of yeast strains, Torulaspora delbrueckii IFO 10921 was selected. The collected cells of this strain, obtained by an incubation in a glucose medium, smoothly reduced only the isolated carbonyl group of the (S)-enantiomer, while the (R)-enantiomer remained intact. Starting from both enantiomers ( approximately 70% ee) prepared by an established proline-mediated asymmetric Robinson annulation, the reduction with T. delbrueckii gave the (R)-enantiomer (98% ee) and the corresponding alcohol (4aS,5S)-4,4a, 5,6,7,8-hexahydro-5-hydroxy-4a-methyl-2(3H)-naphthalenone (94% ee, 94% de) in preparative scale in nearly quantitative yields. An approach for the asymmetric synthesis of the Wieland-Miescher ketone was also successful. 2-Methyl-2-(3-oxobutyl)-1,3-cyclohexanedione, the prochiral precursor, was reduced with this strain to give a cyclic acetal form of (2S, 3S)-3-hydroxy-2-methyl-2-(3-oxobutyl)cyclohexanone, in a stereomerically pure form.

Nobutaka Funa

Papers

Access to Wieland-Miescher ketone in an enantiomerically pure form by a kinetic resolution with yeast-mediated reduction.