Nickel/Photoredox Dual-Catalyzed Regiodivergent Aminoalkylation of Unactivated Alkyl Halides

A mild and regiodivergent aminoalkylation of unactivated alkyl halides is disclosed via a dual photoredox/nickel catalysis. Bipyridyl-type ligands without an ortho-substituent control the site-selective coupling at the original position, while ortho-disubstituted ligands tune the site-selectivity at...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2023-10, Vol.145 (42), p.23385-23394
Main Authors: Wang, Wenlong, Yan, Xueyuan, Ye, Fu, Zheng, Songlin, Huang, Genping, Yuan, Weiming
Format: Article
Language:English
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Summary:A mild and regiodivergent aminoalkylation of unactivated alkyl halides is disclosed via a dual photoredox/nickel catalysis. Bipyridyl-type ligands without an ortho-substituent control the site-selective coupling at the original position, while ortho-disubstituted ligands tune the site-selectivity at a remote, unprefunctionalized position. Mechanistic studies combined with DFT calculations give insight into the mechanism and the origins of the ligand-controlled regioselectivity. Notably, this redox-neutral, regiodivergent alkyl–alkyl coupling features mild conditions, broad substrate scope for both alkyl coupling partners, and excellent site-selectivity and offers a straightforward way for α-alkylation of tertiary amines to synthesize structurally diverse alkylamines and value-added amino acid derivatives.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.3c09705