Nickel‐Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C−N Bond Activation. Issue 30 (3rd June 2016)

• Record Type: Journal Article
• Authors: Hu, Jiefeng; Zhao, Yue; Liu, Jingjing; Zhang, Yemin; Shi, Zhuangzhi
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 30(2016)
• Page Start: 8718
• Page End: 8722
• Publication Date: 2016-06-03
• Subjects: amides -- boron -- decarbonylation -- nickel -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201603068
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A nickel/N‐heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B2 nep2 by C−N bond activation. This transformation shows good functional‐group compatibility and can serve as a powerful synthetic tool for late‐stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was first confirmed by X‐ray analysis. Furthermore, the decarbonylative process was also observed. These findings confirm the key mechanistic features of the acyl C−N bond activation process. Abstract : Keyed up : A Ni/N‐heterocyclic carbene (NHC) catalytic system has been established for the title reaction, which proceeds by C−N bond activation. As a key intermediate, the structure of an acyl nickel complex was confirmed by X‐ray analysis. The structure displays square‐planar geometry, stabilized by two NHC ligands in trans position. These findings confirm the key mechanistic features of the acyl C−N bond activation process. Boc= tert ‐butoxycarbonyl, nep=neopentyl glycolato.