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Nickel(II/IV) manifold enables room-temperature C(sp3)–H functionalization

Roberts, CC, Chong, E, Kampf, JW, Canty, AJ, Ariafard, A ORCID: 0000-0003-2383-6380 and Sanford, MS 2019 , 'Nickel(II/IV) manifold enables room-temperature C(sp3)–H functionalization' , Journal of the American Chemical Society, vol. 141, no. 49 , pp. 19513-19520 , doi: 10.1021/jacs.9b11999.

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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 ∼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.

Item Type: Article
Authors/Creators:Roberts, CC and Chong, E and Kampf, JW and Canty, AJ and Ariafard, A and Sanford, MS
Keywords: organonickel, C-H activation, nickel(IV), DFT, organometallic mechanism
Journal or Publication Title: Journal of the American Chemical Society
Publisher: Amer Chemical Soc
ISSN: 0002-7863
DOI / ID Number: 10.1021/jacs.9b11999
Copyright Information:

© 2019 American Chemical Society

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