Regiodivergent and stereoselective hydroxyazidation of alkenes by biocatalytic cascades

Jing-Fei Wu; Nan-Wei Wan; Ying-Na Li; Qing-Ping Wang; Bao-Dong Cui; Wen-Yong Han; Yong-Zheng Chen

doi:10.1016/j.isci.2021.102883

Regiodivergent and stereoselective hydroxyazidation of alkenes by biocatalytic cascades

iScience. 2021 Jul 17;24(8):102883. doi: 10.1016/j.isci.2021.102883. eCollection 2021 Aug 20.

Authors

Jing-Fei Wu^{1

2}, Nan-Wei Wan^{1

2}, Ying-Na Li^{1

2}, Qing-Ping Wang^{1

2}, Bao-Dong Cui^{1

2}, Wen-Yong Han^{1

2}, Yong-Zheng Chen^{1

2}

Affiliations

¹ Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, Generic Drug Research Center of Guizhou Province, Green Pharmaceuticals Engineering Research Center of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi, 563000, China.
² Key Laboratory of Basic Pharmacology of Ministry of Education and Joint International Research Laboratory of Ethnomedicine of Ministry of Education, Zunyi Medical University, , Zunyi, 563000, China.

Abstract

Asymmetric functionalization of alkenes allows the direct synthesis of a wide range of chiral compounds. Vicinal hydroxyazidation of alkenes provides a desirable path to 1,2-azidoalcohols; however, existing methods are limited by the control of stereoselectivity and regioselectivity. Herein, we describe a dual-enzyme cascade strategy for regiodivergent and stereoselective hydroxyazidation of alkenes, affording various enantiomerically pure 1,2-azidoalcohols. The biocatalytic cascade process is designed by combining styrene monooxygenase-catalyzed asymmetric epoxidation of alkenes and halohydrin dehalogenase-catalyzed regioselective ring opening of epoxides with azide. Additionally, a one-pot chemo-enzymatic route to chiral β-hydroxytriazoles from alkenes is developed via combining the biocatalytic cascades and Cu-catalyzed azide-alkyne cycloaddition.

Keywords: Biocatalysis; Bioengineering; Biosynthesis.