Metal-free catalytic hydroboration of imine with pinacolborane using a pincer-type phosphorus compound: mechanistic insight and improvement of the reaction.

A mechanistic study of the catalytic hydroboration of imine using a pincer-type phosphorus compound 1NP was performed through the combination of DFT and DLPNO-CCSD(T) calculations. The reaction proceeds through a phosphorus-ligand cooperative catalytic cycle, where the phosphorus center and triamide ligand work in a synergistic manner. First, the pinB-H bond activation by 1NP occurs through the cooperative functions of the phosphorus center and the triamide ligand, leading to a phosphorus-hydride intermediate 2NP. This is the rate-determining step, with the Gibbs energy barrier and Gibbs reaction energy of 25.3 and -17.0 kcal mol -1 , respectively. Subsequently, the hydroboration of phenylmethanimine takes place through a concerted transition state through the cooperative function of the phosphorus center and the triamide ligand. It leads to the final hydroborated product 4 with the regeneration of 1NP. Our computational results reveal that the experimentally isolated intermediate 3NP is a resting state of the reaction. It is formed through the B-N bond activation of 4 by 1NP, rather than via the insertion of the CN double bond of phenylmethanimine into the P-H bond of 2NP. However, this side reaction can be suppressed by utilizing a planar phosphorus compound AcrDipp-1NP as the catalyst, which features steric-demanding substituents on the chelated N atom of the ligand.