Aureobasidium subglaciale F134 is a bifunctional whole-cell biocatalyst for Baeyer-Villiger oxidation or selective carbonyl reduction controllable by temperature

doi:10.1016/j.cjche.2020.06.041

Abstract

Abstract: The microbial production of either ester/lactones or enantio-enriched alcohols through Baeyer-Villiger oxidation or stereoselective reduction of ketones, respectively, is possible by using whole cells of A. subglaciale F134 as a bifunctional biocatalyst. The chemoselective pattern of acetophenone biotransformation catalyzed by these cells can be regulated through reaction temperature, directing the reaction either towards oxidation or reduction products. The Baeyer-Villiger oxidation activity of A. subglaciale F134 whole cells is particularly dependent on reaction temperature. Acetophenone was transformed efficiently to phenol via the primary Baeyer-Villiger product phenyl acetate at 20℃ after 48 h with 100% conversion. In contrast, at 35℃, enantio-enriched (S)-1-phenylethanol was obtained as the sole product with 64% conversion and 89% ee. In addition, A. subglaciale F134 cells also catalyze the selective reduction of various structurally different aldehydes and ketones to alcohols with 40% to 100% yield, indicating broad substrate spectrum and good enantioselectivity in relevant cases. Our study provides a bifunctional biocatalyst system that can be used in Baeyer-Villiger oxidation as well as in asymmetric carbonyl reduction, setting the stage for future work concerning the identification and isolation of the respective enzymes.

Key words: Biocatalysis, Whole cells, Baeyer-Villiger oxidation, Aureobasidium subglaciale, Carbonyl reduction

摘要： The microbial production of either ester/lactones or enantio-enriched alcohols through Baeyer-Villiger oxidation or stereoselective reduction of ketones, respectively, is possible by using whole cells of A. subglaciale F134 as a bifunctional biocatalyst. The chemoselective pattern of acetophenone biotransformation catalyzed by these cells can be regulated through reaction temperature, directing the reaction either towards oxidation or reduction products. The Baeyer-Villiger oxidation activity of A. subglaciale F134 whole cells is particularly dependent on reaction temperature. Acetophenone was transformed efficiently to phenol via the primary Baeyer-Villiger product phenyl acetate at 20℃ after 48 h with 100% conversion. In contrast, at 35℃, enantio-enriched (S)-1-phenylethanol was obtained as the sole product with 64% conversion and 89% ee. In addition, A. subglaciale F134 cells also catalyze the selective reduction of various structurally different aldehydes and ketones to alcohols with 40% to 100% yield, indicating broad substrate spectrum and good enantioselectivity in relevant cases. Our study provides a bifunctional biocatalyst system that can be used in Baeyer-Villiger oxidation as well as in asymmetric carbonyl reduction, setting the stage for future work concerning the identification and isolation of the respective enzymes.

关键词: Biocatalysis, Whole cells, Baeyer-Villiger oxidation, Aureobasidium subglaciale, Carbonyl reduction

Liqun Shen, Ran Cang, Guang Yang, Anqi Zeng, He Huang, Zhigang Zhang. Aureobasidium subglaciale F134 is a bifunctional whole-cell biocatalyst for Baeyer-Villiger oxidation or selective carbonyl reduction controllable by temperature[J]. Chinese Journal of Chemical Engineering, 2020, 28(12): 3044-3051.

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