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Nickel(II/IV) manifold enables room-temperature C(sp3)–H functionalization
journal contribution
posted on 2023-05-20, 08:59 authored by Roberts, CC, Chong, E, Kampf, JW, Allan CantyAllan Canty, Alireza AriafardAlireza Ariafard, Sanford, MSThis 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 ∼3 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.
History
Publication title
Journal of the American Chemical SocietyVolume
141Issue
49Pagination
19513-19520ISSN
0002-7863Department/School
School of Natural SciencesPublisher
Amer Chemical SocPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
© 2019 American Chemical SocietyRepository Status
- Restricted