Computational study of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO2: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions

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.