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Nickel‐Catalyzed Mono‐Selective α‐Arylation of Acetone with Aryl Chlorides and Phenol Derivatives
Author(s) -
Derhamine Sary Abou,
Krachko Tetiana,
Monteiro Nuno,
Pilet Guillaume,
Schranck Johannes,
Tlili Anis,
Amgoune Abderrahmane
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202006826
Subject(s) - catalysis , acetone , nickel , aryl , phenol , chemistry , ligand (biochemistry) , combinatorial chemistry , organic chemistry , biochemistry , alkyl , receptor
Abstract The challenging nickel‐catalyzed mono‐α‐arylation of acetone with aryl chlorides, pivalates, and carbamates has been achieved for the first time. A nickel/Josiphos‐based catalytic system is shown to feature unique catalytic behavior, allowing the highly selective formation of the desired mono‐α‐arylated acetone. The developed methodology was applied to a variety of (hetero)aryl chlorides including biologically relevant derivatives. The methodology has been extended to the unprecedented coupling of acetone with phenol derivatives. Mechanistic studies allowed the isolation and characterization of key Ni 0 and Ni II catalytic intermediates. The Josiphos ligand is shown to play a key role in the stabilization of Ni II intermediates to allow a Ni 0 /Ni II catalytic pathway. Mechanistic understanding was then leveraged to improve the protocol using an air‐stable Ni II pre‐catalyst.