Nickel-Catalyzed Site-Selective Amidation of Unactivated C(sp3)H Bonds

• Published in: Chemistry : a European journal Vol. 20; no. 31; pp. 9530 - 9533
• Main Authors: Wu, Xuesong, Zhao, Yan, Ge, Haibo
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 28-07-2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Aliphatic compounds; amidation; Amides; Beta; Carbon; Catalysis; Chemical bonds; Chemistry; CH bond functionalization; Dehydrogenation; Nickel; site selectivity; β-lactams; amidation; nickel; β-lactams; CH bond functionalization; site selectivity
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201403356

Intramolecular dehydrogenative cyclization of aliphatic amides was achieved on unactivated sp3 carbon atoms by a nickel‐catalyzed CH bond functionalization process with the assistance of a bidentate directing group. The reaction favors the CH bonds of β‐methyl groups over the γ‐methyl or β‐methylene groups. Additionally, a predominant preference for the β‐methyl CH bonds over the aromatic sp2 CH bonds was observed. Moreover, this process also allows for the effective functionalization of benzylic secondary sp3 CH bonds.
β‐Lactams from nickel catalysis: Intramolecular dehydrogenative cyclization of aliphatic amides was achieved on unactivated sp3 carbon atoms by a nickel‐catalyzed CH bond functionalization process with the assistance of a bidentate directing group (see scheme).