Stereoselective cyano translocation reaction enabled by photoenzymatic catalysis

Functional-group translocation constitutes a powerful strategy in organic synthesis, allowing precise modification of molecular architectures and functional group positions. Nevertheless, methodologies capable of delivering precise stereocontrol during such migrations remain exceedingly scarce. Herein, we present a photoenzymatic strategy for cyano translocation that achieves precise stereocontrol. The use of stereo-complementary enzymes grants access to both enantiomers, while mechanistic studies and molecular dynamics simulations delineate the origin of stereoselectivity. This work expands the paradigm of transformations that can be rendered asymmetric by photoenzymatic catalysis and provides a new strategy to tackle persistent challenges in organic synthesis.