Organic Chemistry

Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines

Authors

Abstract

A Ni-catalyzed reductive cross-coupling of heteroaryl imines with C(sp3) electrophiles for the preparation of heterobenzylic amines is reported. This umpolung-type alkylation proceeds under mild conditions, avoids the pre-generation of organometallic reagents, and exhibits good functional group tolerance. Mechanistic studies are consistent with the imine substrate acting as a redox-active ligand upon coordination to a low-valent Ni center. The resulting bis(2-imino)heterocycle·Ni complexes can engage in alkylation reactions with a variety of C(sp3) electrophiles, giving heterobenzylic amine products in good yields.

Version notes

Updated draft with additional mechanistic experiments and electrochemical scope.

Content

Thumbnail image of 2022-05-16-ChemRxiv.pdf

Supplementary material

Thumbnail image of 2022-5-23_ImineExp_SI_Combined.pdf
Supporting Information
Experimental procedures, characterization data, computational details