Modification and Unexpected Reactivity of 2-Borylbenzaldimines: Acylated and Silylated Derivatives as Well as Dimeric Compounds

Abstract

Various novel N-alkyl and N-benzyl 2-borylbenzaldimines 3 were prepared by condensation of 2-(dimesitylboryl)benzaldehyde (1) with amines. Further functionalization of compound 3e was possible by deprotonation and subsequent regioselective reaction with electrophiles to give compounds 4. Applying similar conditions to 3a led to the unexpected formation of hitherto unknown dimeric compounds (5 and 6). All structural types were fully characterized, including by X-ray diffraction (XRD). Furthermore, quantum chemical calculations on the SCS-MP2 and DFT levels gave insights into the reaction mechanisms and the stereoselectivity. The B/N bonding situation in these molecules was analyzed using Wiberg bond indices. Preliminary UV-vis and fluorescence measurements indicate that the substitution reaction leading to compounds 4 can be utilized to tune the photophysical properties of these compounds.