Synthesis of α‐N‐Heteroaryl Ketones by Nickel‐Catalyzed Chemo‐, Regio‐ and Enantioselective Carbonylation of Alkenes and <i>N</i>‐Alkenyl Heteroarenes

Abstract Enantioenriched α‐aminoketones serve as important substructures in life science and precursors for the synthesis of diverse value‐added targets in organic and biochemistry. However, direct access to enantioenriched α‐aminoketones from simple and readily available starting materials remains a formidable challenge. Herein, we report an unprecedented nickel‐catalyzed asymmetric cross‐coupling protocol for the synthesis of enantioenriched α‐ N ‐heteroaryl ketones from alkenes and enamines in the presence of a carbon monoxide surrogate. The success of this reaction relies on the sorting of two different alkenes along with the control of regio‐ and enantioselectivity. This reductive‐oxidative carbonylation of enamines and unactivated alkenes featuring the use of a carbon monoxide surrogate allows for the gas‐free streamlined assembly of enantioenriched α‐ N ‐heteroaryl ketones from two distinct alkenes.