Journal
MOLECULES
Volume 25, Issue 5, Pages -Publisher
MDPI
DOI: 10.3390/molecules25051141
Keywords
Ni-III and Ni-IV chemistry; cross-coupling reactions; C-H bond functionalization; trifluoromethylation; fluorination
Funding
- Institut de Chimie de Toulouse
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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 M-0/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.
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