Asymmetric catalysis by chiral FLPs: A computational mini-review

Abstract

Steric hindrance in Lewis acid (LA) and Lewis base (LB) obstruct the Lewis acid–base adduct formation, and the pair was termed as frustrated Lewis pair (FLP). In the past 16 years, the field of enantioselective catalysis by chiral FLPs has been slowly growing. It was shown that chiral LAs are significant as they are involved in the hydrogen transfer (HT) step to the imine, resulting in enantioselectivity. After H₂ activation, the borohydride can exist in a number of plausible conformations and their stability is governed by the presence of noncovalent interaction through C–H····π and π····π interactions. However, LBs are not ideal for asymmetric induction as they compete with the imine substrate as a counter LB. Further, the proton transfer from chiral LB to the imine does not induce any chirality as chirality develops in the HT step. However, intramolecular FLPs with chiral scaffold are very efficient as they possess an optimum distance between LA and LB, which facilitates the H₂ activation but precludes the adduct formation of the small molecules substrate with the LA component. This mini-review summarizes computational investigation involving chiral LA and LB, and discusses intramolecular FLPs in the enantioselective catalysis.