Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Abstract The development of enantioselective alkyl–alkyl cross‐couplings with coinstantaneous formation of a stereogenic center without the use of sensitive organometallic species is attractive yet challenging. Herein, we report the intermolecular regio‐ and enantioselective formal hydrofunctionalizations of acrylamides, forging a stereogenic center α‐position to the newly formed C sp3 –C sp3 bond for the first time. The use of a newly developed chiral ligand enables the electronically‐reversed formal hydrofunctionalizations, including hydroalkylation, hydrobenzylation, and hydropropargylation, offering an efficient way to access diverse enantioenriched amides with a tertiary α‐stereogenic carbon center which is facile to racemize. This operationally simple protocol allows for the anti‐Markovnikov enantioselective hydroalkylation, and unprecedented hydrobenzylation, hydropropargylation under mild conditions with excellent functional group compatibility, delivering a wide range of amides with excellent levels of enantioselectivity.