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Intramolecular Stereoselective Stetter Reaction Catalyzed by Benzaldehyde Lyase

Xiaoyang Chen, Zhiguo Wang, Yujiao Lou, Yongzhen Peng, Qiaoyan Zhu, Jian Xu, Qi Wu

2021Angewandte Chemie International Edition36 citationsDOI

Abstract

The reliable design and prediction of enzyme promiscuity to access transformations not observed in nature remains a long-standing challenge. Herein, we present the first example of an intramolecular stereoselective Stetter reaction catalyzed by benzaldehyde lyase, guided by the rational structure screening of various ThDP-dependent enzymes using molecular dynamics (MD) simulations. After optimization, high productivity (up to 99 %) and stereoselectivity (up to 99:1 e.r.) for this novel enzyme function was achieved.

Topics & Concepts

StereoselectivityBenzaldehydeIntramolecular forceChemistryCatalysisUmpolungOrganic chemistryStereochemistryNucleophileN-Heterocyclic Carbenes in Organic and Inorganic ChemistryCyclopropane Reaction MechanismsSynthetic Organic Chemistry Methods