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Ni‐Catalyzed α‐Alkylation of Unactivated Amides and Esters with Alcohols by Hydrogen Auto‐Transfer Strategy
Author(s) -
Midya Siba P.,
Rana Jagannath,
Pitchaimani Jayaraman,
Nandakumar Avanashiappan,
Madhu Vedichi,
Balaraman Ekambaram
Publication year - 2018
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201801443
Subject(s) - alkylation , chemistry , catalysis , pincer movement , nickel , organic chemistry , salt (chemistry) , hydrogen bond , transition metal , primary (astronomy) , hydrogen , combinatorial chemistry , molecule , physics , astronomy
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.