Theoretical Study of the Borono-Mannich Reaction with Pinacol Allenylboronate

A density functional theory study of the mechanism of the Borono-Mannich reaction using benzylamine and piperidine as representative examples of primary and secondary amines with pinacol allenylboronate is presented. The study shows that both reactions progress through coordination between the boron and the phenolic oxygen. Ring size strain and hydrogen bond activation appear to determine the observed divergent regioselectivity. In the case of benzylamine, the eight-membered ring transition structure that leads to the propargylamine exhibits a hydrogen bond between the hydrogen attached to the nitrogen and the phenolic oxygen (γ-attack), whereas for piperidine a hydrogen bond between the hydrogen on the imine carbon and one of the oxygens of the pinacol group was observed in the six-membered ring transition structure toward the allenylamine (α-attack).