Nickel‐Catalyzed Mono‐Selective α‐Arylation of Acetone with Aryl Chlorides and Phenol Derivatives.

Derhamine, Sary Abou; Krachko, Tetiana; Monteiro, Nuno; Pilet, Guillaume; Schranck, Johannes; Tlili, Anis; Amgoune, Abderrahmane

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 Ni0 and NiII catalytic intermediates. The Josiphos ligand is shown to play a key role in the stabilization of NiII intermediates to allow a Ni0/NiII catalytic pathway. Mechanistic understanding was then leveraged to improve the protocol using an air‐stable NiII pre‐catalyst.

PHENOL derivatives; ARYL chlorides; ACETONE; CARBAMATES; OXIDATIVE addition

Angewandte Chemie, 2020, Vol 132, Issue 43, p19110

0044-8249

Academic Journal

10.1002/ange.202006826