Premium
Nickel‐Catalyzed Allylic Alkylation with Diarylmethane Pronucleophiles: Reaction Development and Mechanistic Insights
Author(s) -
Sha ShengChun,
Jiang Hui,
Mao Jianyou,
Bellomo Ana,
Jeong Soo A.,
Walsh Patrick J.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201507494
Subject(s) - nucleophile , allylic rearrangement , chemistry , catalysis , palladium , tsuji–trost reaction , nickel , substitution reaction , alkylation , leaving group , combinatorial chemistry , medicinal chemistry , organic chemistry
Palladium‐catalyzed allylic substitution reactions are among the most efficient methods to construct C−C bonds between sp 3 ‐hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a “soft”‐nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with “hard” nucleophiles, which attack the metal before C−C bond formation. Introduced herein is a rare nickel‐based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft‐nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising.