Unveiling Hetero-Enyne Reactivity of Aryliminoboranes: Dearomative Hetero-Diels-Alder-Like Reactions

Being isoelectronic with alkynes, iminoboranes with a polar B≡N triple bond have been exclusively investigated as a potent 1,2-dipole in synthetic chemistry. Herein, we disclose the unprecedented reactivity of aryliminoboranes via the BNCC π conjugation, namely hetero-enyne behavior. This allows for facile dearomative Diels-Alder-like reactions of aryliminoboranes with aldehydes. This cycloaddition features mild conditions, is catalyst-free, and has a broad substrate scope and good functional group tolerance. Kinetic and computational studies reveal its second-order reaction and concerted cyclization mechanism. This report unveils new synthetic application of iminoboranes beyond their classical reaction patterns.