Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 5, Pages 1251-1255Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201710676
Keywords
C-H activation; high-valent metal-oxo complexes; manganese porphyrins; nucleophilic fluorination; radical halogenation
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Funding
- US National Science Foundation [CHE-1464578]
- BMS Center for Molecular Synthesis at Princeton University
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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-Mn-V 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.
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