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

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.