C-N and C-O Bond Formation in Copper-Catalyzed/Mediated sp3C-H Activation: Mechanistic Studies from Experimental and Computational Aspects

Yuhang Yang, Fei Cao, Linbin Yao, Tao Shi, Bencan Tang, Yoichiro Kuninobu, Zhen Wang

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)9713-9726
Number of pages14
JournalJournal of Organic Chemistry
Volume85
Issue number15
DOIs
Publication statusPublished - Aug 7 2020

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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