铜催化配体调控烯烃酰基硼化反应的机理研究

ransition metal catalyzed activation and conversion of carbon monoxide (CO) is an effective mechanism for synthesizing organic compounds containing carbonyl groups and extending carbon chains, while also achieving the transformation of inorganic carbon to organic carbon during this process. Among them, CO is often activated to form acyl-metal species, and controlling the reaction direction of this species is crucial for obtaining ideal organic products. Therefore, it is imperative to research the reaction mechanism of acyl-metal species under different ligands. In order to investigate the reactivity and chemoselectivity of acyl-metal species under different ligand coordination, this study chose the ligand controlled copper catalyzed acyl boronation of olefins reaction reported by the Wu Xiaofeng group as the template reaction. Through theoretical calculations, we explored which of the three reactions, protonation, carbonyl intramolecular insertion, and 1,2 copper-migration, is more likely to occur in acyl-copper under the coordination of N-heterocyclic carbene ligand (NHC ligand) and bidentate tertiary phosphine ligand (DPPE ligand). And explain the reason for ligand controlled chemoselectivity through HOMO orbital analysis, NPA charge analysis, and IGMH analysis. Ultimately, it was found that the combination of electrical and non-bonding interactions led to the easier protonation of acyl copper to aldehydes under NHC ligand coordination, while acyl copper was more prone to carbonyl intramolecular insertion to cyclopropane product under DPPE ligand coordination.