Rhodium-Catalyzed Enantio- and Diastereoselective Carboami-dation of Bicyclic Olefins toward Construction of Remote Chiral Centers and Axis

The precise control of multiple chiral elements through a single step catalytic process remains a significant challenge in asymmetric catalysis. Reported herein is rhodium-catalyzed three-component asymmetric carboamidation between aryl boronic acid, achiral strain-activated symmetric bicyclic olefins bearing a prochiral C-N or N-N axis, and dioxazolones. The reaction proceeded effectively in excellent enantio- and diastereoselectivity under mild conditions to produce the bicyclic framework with six contiguous chiral centers as well as a N-N or C-N chiral axis. The reaction featured excellent functional group tolerance, chemoselectivity, and stereoselectivity. Mechanistic studies indicated that the coupling system proceeded via initial transmetalation, followed by stereo-determining migratory insertion into the olefin and electrophilic amidation. (https://doi.org/10.1007/s11426-023-1646-0)

Congratulations to Jinlei Wang.