Vanadium-Based Enantioselective Electrophotocatalysis of Protic C(sp 3 )-H Bonds

The construction of valuable 3D molecular architectures from easy-to-handle stable bulk chemicals has long been a target in chemical society. However, the highly reactive intermediates generated in situ pose significant challenges for achieving enantioselective control. To address these challenges, novel catalysts must be developed. This report describes a multifunctional vanadium electrophotocatalyst that serves as a photosensitizer and C(sp 3 )-H activation catalyst precursor to activate protic C(sp 3 )-H bonds. Notably, it also acts as a chiral metal catalyst to enable enantioselective control. The optimized protocol tolerates a diverse array of readily available feedstocks (e.g., acetone, acetonitrile, dichloromethane) with various functional groups, which can be enantioselectively incorporated onto a C═C double bond at looxidation potential (around 0.40 V vs Ag/AgCl). The nonclassical toolkit described herein is characterized by high sustainability, diverse protic C(sp 3 )-H compounds, and excellent enantioselectivity without requiring external chemical oxidants, thus opening new synthetic routes via unique reactivities.