Nickel Catalysis via SH2 Homolytic Substitution: The Double Decarboxylative Cross-Coupling of Aliphatic Acids

Artem V. Tsymbal, Lorenzo Delarue Bizzini, David W.C. Macmillan

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Cross-coupling platforms are traditionally built around a sequence of closed-shell steps, such as oxidative addition, transmetalation, and reductive elimination. Herein, we describe a dual photo/nickel catalytic manifold that performs cross-coupling via a complementary sequence involving free radical generation, radical sorting via selective binding to a Ni(II) center, and bimolecular homolytic substitution (SH2) at a high-valent nickel-alkyl complex. This catalytic manifold enables the hitherto elusive cross-coupling of diverse aliphatic carboxylic acids to generate valuable C(sp3)-C(sp3)-products. Notably, the powerful SH2 mechanism provides general access to sterically encumbered quaternary carbon centers, addressing a long-standing challenge in fragment coupling chemistry.

Original languageEnglish (US)
Pages (from-to)21278-21286
Number of pages9
JournalJournal of the American Chemical Society
Volume144
Issue number46
DOIs
StatePublished - Nov 23 2022

All Science Journal Classification (ASJC) codes

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

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