Catalytic C(sp3)-H alkylation via an iron carbene intermediate

Jennifer R. Griffin, Chloe I. Wendell, Jacob A. Garwin, M. Christina White

Research output: Contribution to journalArticlepeer-review


The catalytic transformation of a C(sp3)-H bond to a C(sp3)-C bond via an iron carbene intermediate represents a long-standing challenge. Despite the success of enzymatic and small molecule iron catalysts mediating challenging C(sp3)-H oxidations and aminations via high-valent iron oxos and nitrenes, C(sp3)-H alkylations via isoelectronic iron carbene intermediates have thus far been unsuccessful. Iron carbenes have been inert, or shown to favor olefin cyclopropanation and heteroatom-hydrogen insertion. Herein we report an iron phthalocyanine-catalyzed alkylation of allylic and benzylic C(sp3)-H bonds. Mechanistic investigations support that an electrophilic iron carbene mediates homolytic C-H cleavage and rebounds from the resulting organoiron intermediate to form the C-C bond; both steps are tunable via catalyst modifications. These studies suggest that for iron carbenes, distinct from other late metal carbenes, C-H cleavage is partially rate-determining and must be promoted to effect reactivity.

Original languageEnglish (US)
Pages (from-to)13624-13627
Number of pages4
JournalJournal of the American Chemical Society
Issue number39
StatePublished - Oct 4 2017

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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