DFT Study in an Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity

Abstract In the present study, the mechanism, origin of stereoselectivity, and role of catalyst of the organocatalytic homologation reaction between phenyl boronate and trifluoromethyl diazomethane have been theoretically investigated using the density functional theory (DFT) method. Based on the calculations, the in situ generated ethanol plays significant role in triggering the reaction. Moreover, the [1,2]‐boron migration process is the stereoselectivity‐determining step, with the S ‐configured isomer being generated predominantly. In addition, NCI analysis is performed to disclose the origin of stereoselectivity.