Copper-Catalyzed Ring-Opening Radical Trifluoromethylation of Cycloalkanone Oximes

Zhonglin Liu; Haigen Shen; Haiwen Xiao; Zhentao Wang; Lin Zhu; Chaozhong Li

doi:10.1021/acs.orglett.9b01803

Copper-Catalyzed Ring-Opening Radical Trifluoromethylation of Cycloalkanone Oximes

Org Lett. 2019 Jul 5;21(13):5201-5205. doi: 10.1021/acs.orglett.9b01803. Epub 2019 Jun 18.

Authors

Zhonglin Liu¹, Haigen Shen¹, Haiwen Xiao¹, Zhentao Wang², Lin Zhu¹, Chaozhong Li^{1

3}

Affiliations

¹ Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis , Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road , Shanghai 200032 , P.R. China.
² College of Chemistry and Material Science , Shandong Agricultural University , Taian, Shandong 271018 , P.R. China.
³ School of Materials and Chemical Engineering , Ningbo University of Technology , no. 201 Fenghua Road , Ningbo 315211 , P.R. China.

PMID: 31247800
DOI: 10.1021/acs.orglett.9b01803

Abstract

The copper-catalyzed ring-opening C-trifluoromethylation of cycloalkanone oximes with Zn(CF₃)₂ complexes is described. The reaction proceeds in dichloromethane under mild conditions, providing an efficient and general entry to γ- or δ-CF₃-substituted nitriles via tandem N-O and C(sp²)-C(sp³) bond cleavage and C(sp³)-CF₃ bond formation. The protocol exhibits a broad substrate scope and wide functional group compatibility. A radical mechanism involving the CF₃ transfer from Cu(II)-CF₃ complexes to alkyl radicals is proposed.

Publication types

Research Support, Non-U.S. Gov't