BAr3F-Catalyzed Imine Hydroboration with Pinacolborane Not Requiring the Assistance of an Additional Lewis Base

The rarely used boron Lewis acid tris[3,5-bis-(trifluoromethyl)phenyl]borane (BAr3F) is found to be an excellent catalyst for metal-free hydroboration of imines. In the presence of 1.0 mol % of BAr3F, several ketimines and aldimines undergo hydroboration with pinacolborane (HBpin) at room temperature without the aid of an external Lewis base. BAr3F is more reactive than other Lewis acidic boranes, including the often-used tris(pentafluorophenyl)borane (B(C6F5)(3)). The steric hindrance imparted by the six fluorine atoms ortho to the boron center in B(C6F5)(3) accounts for this. Mechanistic control experiments indicate conventional Lewis acid catalysis involving imine activation and hydride transfer from HBpin.