Understanding the insertion reactions of CO2, aldehyde and alkene into Cu–X (X = B, C, O) bonds

DFT calculations have been performed to study the relative preference of different unsaturated organic molecules (CO2, PhCHO and styrene) for insertion into different Cu–X (X = B, C, O) bonds, which are competing processes in copper-catalyzed three-component boracarboxylation reactions involving CO2 and B2pin2. In this work, the variations in the insertion barriers and in the relative stability of the insertion products have been systematically analyzed and discussed in-depth. Our DFT calculations also allow us to make a prediction that when both aldehyde and styrene are present with CO2 and B2pin2, styrene will undergo the three-component boracarboxylation reaction rather than the aldehyde.