Manganese-Catalyzed Desaturation of N-Acyl Amines and Ethers

Gang Li, Patrick A. Kates, Andrew K. Dilger, Peter T. Cheng, William R. Ewing, John T. Groves

Research output: Contribution to journalArticle

4 Scopus citations

Abstract

Enamines and enol ethers are versatile synthons for chemical synthesis. While several methods have been developed to access such molecules, prefunctionalized starting materials are usually required, and direct desaturation methods remain rare. Herein, we report direct desaturation reactions of N-protected cyclic amines and cyclic ethers using a mild I(III) oxidant, PhI(OAc)2, and an electron-deficient manganese pentafluorophenylporphyrin catalyst, Mn(TPFPP)Cl. This system displays high efficiency for α,β-desaturation of various cyclic amines and ethers. Mechanistic probes suggest that the desaturation reaction occurs via an initial α-C-H hydroxylation pathway, which serves to protect the product from overoxidation.

Original languageEnglish (US)
Pages (from-to)9513-9517
Number of pages5
JournalACS Catalysis
Volume9
Issue number10
DOIs
StatePublished - Oct 4 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • C-H activation
  • desaturation
  • high-valent metal-oxo complexes
  • homogeneous catalysis
  • manganese porphyrins

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    Li, G., Kates, P. A., Dilger, A. K., Cheng, P. T., Ewing, W. R., & Groves, J. T. (2019). Manganese-Catalyzed Desaturation of N-Acyl Amines and Ethers. ACS Catalysis, 9(10), 9513-9517. https://doi.org/10.1021/acscatal.9b03457