C-H Alkylation via Multisite-Proton-Coupled Electron Transfer of an Aliphatic C-H Bond

Carla M. Morton, Qilei Zhu, Hunter Ripberger, Ludovic Troian-Gautier, Zi S.D. Toa, Robert R. Knowles, Erik J. Alexanian

Research output: Contribution to journalArticle

18 Scopus citations

Abstract

The direct, site-selective alkylation of unactivated C(sp3)-H bonds in organic substrates is a long-standing goal in synthetic chemistry. General approaches to the activation of strong C-H bonds include radical-mediated processes involving highly reactive intermediates, such as heteroatom-centered radicals. Herein, we describe a catalytic, intermolecular C-H alkylation that circumvents such reactive species via a new elementary step for C-H cleavage involving multisite-proton-coupled electron transfer (multisite-PCET). Mechanistic studies indicate that the reaction is catalyzed by a noncovalent complex formed between an iridium(III) photocatalyst and a monobasic phosphate base. The C-H alkylation proceeds efficiently using diverse hydrocarbons and complex molecules as the limiting reagent and represents a new approach to the catalytic functionalization of unactivated C(sp3)-H bonds.

Original languageEnglish (US)
Pages (from-to)13253-13260
Number of pages8
JournalJournal of the American Chemical Society
Volume141
Issue number33
DOIs
StatePublished - Aug 21 2019

All Science Journal Classification (ASJC) codes

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

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    Morton, C. M., Zhu, Q., Ripberger, H., Troian-Gautier, L., Toa, Z. S. D., Knowles, R. R., & Alexanian, E. J. (2019). C-H Alkylation via Multisite-Proton-Coupled Electron Transfer of an Aliphatic C-H Bond. Journal of the American Chemical Society, 141(33), 13253-13260. https://doi.org/10.1021/jacs.9b06834