1613614-64-4Relevant academic research and scientific papers
C-N and C-O Bond Formation in Copper-Catalyzed/Mediated sp3C-H Activation: Mechanistic Studies from Experimental and Computational Aspects
Yang, Yuhang,Cao, Fei,Yao, Linbin,Shi, Tao,Tang, Bencan,Kuninobu, Yoichiro,Wang, Zhen
supporting information, p. 9713 - 9726 (2020/09/03)
Mechanistic studies on Cu-catalyzed/mediated sp3 C-H amidation and acetoxylation are investigated from experimental and computational aspects. The concerted metalation-deprotonation (CMD) mechanism rather than a radical-involved pathway is proved to occur in amidation and acetoxylation reactions, and this is the rare example of the CMD mechanism involved in the more challenging sp3 C-H activations. Theoretical calculations demonstrated that CMD is the rate-determining step either for methylic or benzylic positions in amidation and acetoxylation reactions, and intermolecular nucleophilic addition of acetate anions is more favorable than the ring opening of β-lactams and intramolecular acetoxylation. These mechanistic studies on the divergent and condition-dependent product formation are critical for developing Cu-promoted C-H functionalization via the CMD mechanism.
Copper-catalyzed site-selective intramolecular amidation of unactivated C(sp3)-H bonds
Wu, Xuesong,Zhao, Yan,Zhang, Guangwu,Ge, Haibo
, p. 3706 - 3710 (2014/04/17)
The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp3 C-H bond functionalization process. The reaction favors predominantly the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds. Moreover, a preference for activating sp3 C-H bonds of β-methyl groups, via a five-membered ring intermediate, over the aromatic sp2 C-H bonds was also observed in the cyclometalation step. Additionally, sp3 C-H bonds of unactivated secondary sp3 C-H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms. Getting ahead on tams: The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp 3 C-H bond functionalization process to deliver β-lactams. The reaction favors the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds, as well as aromatic C(sp2)-H bonds and unactivated secondary C(sp3)-H bonds of rings.
Nickel-catalyzed site-selective amidation of unactivated C(sp 3)-H bonds
Wu, Xuesong,Zhao, Yan,Ge, Haibo
supporting information, p. 9530 - 9533 (2014/08/18)
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).
