High-Valent NiIII and NiIV Species Relevant to C-C and C-Heteroatom Cross-Coupling Reactions: State of the Art

Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry
Noel Nebra

Abstract

Ni catalysis constitutes an active research arena with notable applications in diverse fields. By analogy with its parent element palladium, Ni catalysts provide an appealing entry to build molecular complexity via cross-coupling reactions. While Pd catalysts typically involve a M0/MII redox scenario, in the case of Ni congeners the mechanistic elucidation becomes more challenging due to their innate properties (like enhanced reactivity, propensity to undergo single electron transformations vs. 2e- redox sequences or weaker M-Ligand interaction). In recent years, mechanistic studies have demonstrated the participation of high-valent NiIII and NiIV species in a plethora of cross-coupling events, thus accessing novel synthetic schemes and unprecedented transformations. This comprehensive review collects the main contributions effected within this topic, and focuses on the key role of isolated and/or spectroscopically identified NiIII and NiIV complexes. Amongst other transformations, the resulting NiIII and NiIV compounds have efficiently accomplished: i) C-C and C-heteroatom bond formation; ii) C-H bond functionalization; and iii) N-N and C-N cyclizative couplings to forge heterocycles.

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Citations

Mar 29, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Joaquín García-Álvarez
Jun 17, 2020·Journal of the American Chemical Society·Oriol PlanasJosep Cornella
Nov 5, 2020·Journal of the American Chemical Society·Franck Le VaillantJosep Cornella
Oct 13, 2021·Inorganic Chemistry·Sam YruegasCaleb D Martin

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Methods Mentioned

BETA
electron paramagnetic resonance
nuclear
X-ray
NMR
1

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