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Updated: Sep 5, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines
Raymond F Turro1, Marco Brandstätter1, Sarah E Reisman1
1The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Abstract:
The preparation of heterobenzylic amines by a Ni-catalyzed reductive cross-coupling between heteroaryl imines and C(sp3 ) electrophiles 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.
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