Base‐Assisted C−H Bond Cleavage in Cross‐Coupling: Recent Insights into Mechanism, Speciation, and Cooperativity

Autor: Long Wang, Jessica Sampson, Brad P. Carrow
Rok vydání: 2019
Předmět:
Zdroj: Isr J Chem
ISSN: 1869-5868
0021-2148
DOI: 10.1002/ijch.201900095
Popis: This review analyzes recent mechanistic studies that have provided new insights into how the structure of a metal complex influences the rate and selectivity of base-assisted C-H cleavage. Partitioning a broader mechanistic continuum into classes delimited by the polarization between catalyst and substrate during C-H cleavage is postulated as a method to identify catalysts favoring electrophilic or nucleophilic reactivity patterns, which may be predictive based on structural features of the metal complex (i.e., oxidation state, d-electron count, charge). Multi-metallic cooperativity and polynuclear speciation also provide new avenues to affect energy barriers for C-H cleavage and site selectivity beyond the limitations of single metal catalysts. An improved understanding of mechanistic nuances and structure-activity relationships on this important bond activation step carries important implications for efficiency and controllable site selectivity in non-directed C-H functionalization.
Databáze: OpenAIRE
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