Computational study of Cu-catalyzed 1, 2-hydrocarboxylation of 1, 3-dienes with CO2: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions. Issue 8 (18th March 2022) - Hu, Yanlei
Abstract : The detailed mechanism of Cu-catalyzed 1, 2-hydrocarboxylation of 1, 3-dienes and origin of Cu-boryl additions have been investigated. Abstract : The mechanism and origin of regioselectivity of Cu-catalyzed 1, 2-hydrocarboxylation of 1, 3-dienes with CO2 were computationally investigated. The results show that CO2 not only acts as a carboxylation reagent, but also plays a critical role in the process of generating the key allyl copper intermediate, which is the active species for 1, 3-diene carboxylation with CO2 . The energy decomposition analysis indicates that Pauli repulsion is the dominant factor for controlling the regioselectivity of Cu–Bpin additions with 1, 3-dienes.