Selective C−H Halogenation with a Highly Fluorinated Manganese Porphyrin

Gang Li, Andrew K. Dilger, Peter T. Cheng, William R. Ewing, John Taylor Groves

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

The selective C−H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C−H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-MnV species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step.

Original languageEnglish (US)
Pages (from-to)1251-1255
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number5
DOIs
StatePublished - Jan 26 2018

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • C−H activation
  • high-valent metal–oxo complexes
  • manganese porphyrins
  • nucleophilic fluorination
  • radical halogenation

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