Nickel‐Catalyzed Mono‐Selective α‐Arylation of Acetone with Aryl Chlorides and Phenol Derivatives. Issue 43 (25th August 2020)

• Record Type: Journal Article
• Authors: Derhamine, Sary Abou; Krachko, Tetiana; Monteiro, Nuno; Pilet, Guillaume; Schranck, Johannes; Tlili, Anis; Amgoune, Abderrahmane
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 43(2020)
• Page Start: 18948
• Page End: 18953
• Publication Date: 2020-08-25
• Subjects: Josiphos ligands -- mechanisms -- nickel intermediates -- oxidative addition -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202006826
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : A nickel/Josiphos‐based catalytic system is shown to be very efficient for the mono‐α‐arylation of acetone with (hetero)aryl chlorides and phenol derivatives. Broad functional‐group tolerance was observed, and the desired products were obtained in good to excellent yields. Mechanistic studies allowed the isolation of catalytic intermediates and provided a rationale for the key role of the ligand.