Ligand‐Controlled Copper‐Catalyzed Regiodivergent Carbonylative Synthesis of α‐Amino Ketones and α‐Boryl Amides from Imines and Alkyl Iodides

Regioselective transformation is among the long‐standing challenges in organic synthesis. In this communication, a copper‐catalyzed selectivity controlled regiodivergent borocarbonylation of imines with alkyl iodides has been developed. Various α‐amino ketones and α‐boryl amides were produced in moderate to good yields from the same substrates. The choice of the ligand is key for the regioselectivity control: α‐amino ketones were produced selectively in good yields with (p‐CF3C6H4)3P as the ligand, whereas the corresponding α‐boryl amides were obtained with high regioselectivities when using MeIMes as the ligand. A novel ligand‐controlled copper‐catalyzed borocarbonylation for the selective synthesis of α‐amino ketones and α‐boryl amides from imines and alkyl iodides has been developed. In this catalyst system, the choice of the ligand is key for the regioselectivity control: α‐amino ketones were produced selectively in good yields with (p‐CF3C6H4)3P as the ligand, whereas the corresponding α‐boryl amides were obtained with high regioselectivities when using MeIMes as the ligand.