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

Molecules

Noel Nebra¹ 

[1] Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse, France;

关键词: niⁱⁱⁱ and ni^iv chemistry;    cross-coupling reactions;    c–h bond functionalization;    trifluoromethylation;    fluorination;   

DOI  :  10.3390/molecules25051141

来源: DOAJ

【 摘 要 】

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/M^II 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 Ni^III and Ni^IV 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 Ni^III and Ni^IV complexes. Amongst other transformations, the resulting Ni^III and Ni^IV 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.

【 授权许可】

Unknown