Biphasic one-pot synthesis of two useful and separable compounds using nicotinamide cofactor-requiring enzymes: Syntheses of (S)-4-hydroxyhexanoate and its lactone

Drueckhammer, Dale G.; Sadozai, S. K.; Wong, Chi‐Huey; Roberts, Stanley M.

doi:10.1016/0141-0229(87)90089-5

Cited by 25 publications

(1 citation statement)

References 34 publications

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“…When starting from the corresponding α -keto ester, the biocatalytic reduction proceeds at an impressive substrate input of 198 g/L with 86% conversion, leading to the desired product ( R ) -143 with 82% yield and an excellent enantioselectivity of > 99% ee (Scheme 6.60 ). The synthesis of chiral alcohols by means of this methodology has already been reported in 1981 by Wong and Whitesides [240,241] . A further type of cofactor regeneration related to the one with a GDH is based on the use of a glucose -6 -phosphate dehydrogenase (G -6 -PDH).…”

Section: Reduction Of Ketonesmentioning

confidence: 97%

Enzyme‐Catalyzed Asymmetric Synthesis

Gröger

2010

Catalytic Asymmetric Synthesis

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INTRODUCTIONBiocatalysis has been recognized over the past decades as a highly valuable tool for organic chemists to prepare enantiomerically pure molecules, so -called chiral building blocks, in a highly effi cient way. Besides a multitude of academic work, it is noteworthy that enzyme catalysis belongs to the standard repertoire in industry when facing challenging enantioselective synthetic routes. A broad range of biocatalytic methods is already in use in particular for large -scale manufacture of drug intermediates [1] .The research in the fi eld of enzyme catalysis has already been comprehensively reviewed some years ago [2] . Thus, the focus of the current review is on a selection of (particularly recently developed) enantioselective enzymatic reactions, which turned out to be highly useful and applicable in organic synthesis, fulfi lling criteria such as high productivity, substrate concentrations, conversions, and enantioselectivities. The presented methods are an interesting complementary tool to existing " classic organic " or " chemocatalytic asymmetric " methodologies. Among biocatalytic reactions, both resolution of racemates and asymmetric synthesis starting from prochiral substrates are attractive routes already applied, in part, in industry. A third type of biotechnological approach, which is not a subject of this review, are fermentation processes. A graphical summary of these three types of so -called " white biotechnology " methodologies is given in Scheme 6.1 .Hydrolases are the enzyme class most commonly applied as biocatalysts in organic chemistry. This is mainly due to the accessibility of these enzymes (used, e.g., in the textile and detergents industry), their suitability for transformations in organic media Catalytic Asymmetric Synthesis, Third Edition, Edited by Iwao Ojima 269 270 ENZYME-CATALYZED ASYMMETRIC SYNTHESIS (in particular when using lipases), and the lack of a need for cofactors. However, in recent years, we have also seen an increasing tendency to apply redox enzymes in organic syntheses as well as lyases in C -C bond formations and transferases. Isomerases also turned out to be very useful in particular in combination with hydrolases for dynamic kinetic resolutions. Thus, a broad range of biotransformations is available for organic chemists. A challenge, however, is the use of ATP cofactor -dependent enzymes, which contribute to only a negligible number of typical organic biotransformations (e.g., due to the high price of ATP).The fi eld of biocatalysis benefi ted signifi cantly from the tremendous progress in molecular biology. Highly effi cient methods for screening and optimization of biocatalysts (by, e.g., directed evolution in the latter case) have been developed, which allows access to tailor -made enzymes. Furthermore, the design of recombinant microorganisms gives access to highly productive whole -cell catalysts, which contain only the desired enzymes in large amount, thus signifi cantly reducing the required biomass for biotransformations compared with the use of...

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Section: Reduction Of Ketonesmentioning

confidence: 97%

Enzyme‐Catalyzed Asymmetric Synthesis

Gröger

2010

Catalytic Asymmetric Synthesis

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Enzyme‐Catalyzed Asymmetric Reduction of Ketones

Gröger

Borchert

Kraußer

et al. 2010

Encyclopedia of Industrial Biotechnology

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The enantioselective transformation of a prochiral C=O double bond into the corresponding reduced CH–OH single bond plays a major role in asymmetric synthesis since this type of transformation represents a straightforward and an atom‐economical approach toward the synthesis of optically active alcohols. Owing to the importance of chiral alcohols in the field of chiral drug production, enantioselective ketone reduction also gained tremendous industrial interest. For the enantioselective reduction of ketones, numerous efficient catalytic routes have been developed up‐to‐date. As outstanding chemocatalytic technologies, metal‐catalyzed asymmetric hydrogenation of ketones and borane reduction are widely applied on industrial scale. Complementing these chemocatalytic technologies for the production of enantiomerically pure alcohols, enantioselective biocatalytic reduction of ketones turned out to be a highly efficient and competitive alternative technology. Notably, biocatalytic ketone technologies already made the “jump” from an interesting academic synthetic tool toward an industrially feasible technology platform. Besides high catalytic efficiency and excellent enantioselectivities, robustness and industrial large‐scale feasibility are further key features of enantioselective ketone reduction processes with biocatalysts. Thus, it is no surprise that the suitability for industrial purpose, in particular, for large‐scale manufacture of enantiomerically pure alcohols as drug intermediates, has been already demonstrated by a broad range of technical applications in the chemical and pharmaceutical industry.

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Reduction Reactions

1995

Enzyme Catalysis in Organic Synthesis

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Biphasic one-pot synthesis of two useful and separable compounds using nicotinamide cofactor-requiring enzymes: Syntheses of (S)-4-hydroxyhexanoate and its lactone

Cited by 25 publications

References 34 publications

Enzyme‐Catalyzed Asymmetric Synthesis

Enzyme‐Catalyzed Asymmetric Synthesis

Enzyme‐Catalyzed Asymmetric Reduction of Ketones

Reduction Reactions

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