Nickel(II/IV) Manifold Enables Room-Temperature C(sp 3)-H Functionalization.

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

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19 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

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation Grant CHE-1111563 as well as CHE-0840456 for X-ray instrumentation. E.C. thanks NSERC for a postdoctoral fellowship. We gratefully acknowledge Emily Norwine for the characterization of product 3-OAc . We also acknowledge the Australian National Computing Infrastructure.

Publisher Copyright:
© 2019 American Chemical Society.

PubMed: MeSH publication types

  • Journal Article

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