Origin of high stereocontrol in olefin cyclopropanation catalyzed by an engineered carbene transferase.

ABSTRACT: Recent advances in metalloprotein engineering have led to the development of a myoglobin-based catalyst, Mb(H64V,V68A), capable of promoting the cyclopropanation of vinylarenes with high efficiency and high diastereo- and enantioselectivity. Whereas many enzymes evolved in nature often exhibit catalytic proficiency and exquisite stereoselectivity, how these features are achieved for a non-natural reaction has remained unclear. In this work, the structural determinants responsible for chiral induction and high stereocontrol in Mb(H64V,V68A)-catalyzed cyclopropanation were investigated via a combination of crystallographic, computational (DFT), and structure-activity analyses. Our results show the importance of steric complementarity and non-covalent interactions involving first-sphere activ

SUBMITTER: Tinoco A 

PROVIDER: S-EPMC6534153 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature