Ni‐Catalyzed α‐Alkylation of Unactivated Amides and Esters with Alcohols by Hydrogen Auto‐Transfer Strategy

A transition‐metal‐catalyzed borrowing hydrogen/hydrogen auto‐transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C‐N and C−C bonds. In this study, a nickel‐catalyzed α‐alkylation of unactivated amides and ester ( tert ‐butyl acetate) is carried out by using primary alcohols under mild conditions. This C−C bond‐forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN‐pincer complex (0.1–1 mol %) and proceeds through hydrogen auto‐transfer, thereby releasing water as the sole byproduct. In addition, N ‐alkylation of cyclic amides under Ni‐catalytic conditions is demonstrated.