Nickel‐Catalyzed Alkoxy–Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers. Issue 49 (7th November 2016)

• Record Type: Journal Article
• Authors: Guo, Lin; Liu, Xiangqian; Baumann, Christoph; Rueping, Magnus
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 49(2016)
• Page Start: 15415
• Page End: 15419
• Publication Date: 2016-11-07
• Subjects: alkylation -- alkylboron reagents -- aromatic methyl ethers -- C−O activation -- nickel catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201607646
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A nickel‐catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B ‐alkyl 9‐BBN and trialkylborane reagents that involves the cleavage of stable C(sp 2 )−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp 2 )−C(sp 3 ) bonds that does not suffer from β‐hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method. Abstract : No side reactions : A nickel‐catalyzed Suzuki‐type alkylation of aryl methyl ethers and methyl enol ethers with B ‐alkyl 9‐BBN and trialkylborane reagents has been developed, which involves the cleavage of highly inert C(sp 2 )−OMe bonds. This transformation provides a versatile way to build C(sp 2 )−C(sp 3 ) bonds that does not suffer from β‐hydride elimination.