Computational Study of the Ir-Catalyzed Formation of Allyl Carbamates from CO.

We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack by the carbamate formed in situ from CO and an amine. A detailed isomeric analysis shows that the rate-determining step differs for the ()- and ()-pathways. These insights are essential for understanding reactions involving enantioselective formation of allyl carbamates from CO.