Nickel(II/IV) Manifold Enables Roomerature C(sp3)-H Functionalization

Courtney C. Roberts, Eugene Chong, Jeff W. Kampf, Allan J. Canty, Alireza Ariafard, Melanie S. Sanford

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

This Article demonstrates a mild oxidatively induced C(sp3)-H activation at a high-valent Ni center. In contrast with most C(sp3)-H activation reactions at NiII, the transformation proceeds at room temperature and generates an isolable NiIV σ-alkyl complex. Density functional theory studies show two plausible mechanisms for this C-H activation process involving triflate-assisted C-H cleavage at either a NiIV or a NiIII intermediate. The former pathway is modestly favored over the latter (by â3 kcal/mol). The NiIV σ-alkyl product of C-H cleavage reacts with a variety of nucleophiles to form C(sp3)-X bonds (X = halide, oxygen, nitrogen, sulfur, or carbon). These stoichiometric transformations can be coupled using N-fluoro-2,4,6-trimethylpyridinium triflate as a terminal oxidant in conjunction with chloride as a nucleophile to achieve a proof-of-principle NiII/IV-catalyzed C(sp3)-H functionalization reaction.

Original languageEnglish (US)
Pages (from-to)19513-19520
Number of pages8
JournalJournal of the American Chemical Society
Volume141
Issue number49
DOIs
StatePublished - Dec 11 2019
Externally publishedYes

PubMed: MeSH publication types

  • Journal Article
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

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