Structural Dynamics and Stereoselectivity of Chiral Benzylideneamine N,C-Chelate Borane Photo-Thermal Isomerization

New chiral N,C-chelate organoboron compounds based on benzylideneamines (bza) with the general formula of B(bza-R)Mes₂ (R=H or Me; Mes=mesityl) are reported. A chiral substituent group R- or S-CH(CH₃ )Ph (Ph=phenyl) was introduced to the imine center, which imposed a previously unobserved pseudo- or axial-chirality on the BMes₂ , creating distinct diastereomers. NMR spectroscopic studies established that the diastereomers undergo slow exchange in solution at ambient temperature. The chiral N,C-chelate B(bza-R)Mes₂ molecules undergo photoisomerization in the same manner as their non-chiral analogues, generating chiral BN-cyclooctatriene (BN-COT) derivatives. Most significantly, by tracking the photoisomerization with circular dichroism (CD) and ¹ H NMR spectra along with time-dependent density functional theory (TD-DFT) computational studies, the photoisomerization was established to proceed in a highly stereoselective manner, that is, one diastereomer converts exclusively to the corresponding diastereomer product in the photoreaction.