Computational Investigation of Scandium-Based Catalysts for Olefin Hydroaminoalkylation and C–H Addition

Great progress has been achieved in the olefin hydroaminoalkylation by using amines, which is an atom-efficient route for the synthesis of alkylated amine derivatives. However, success in the catalytic olefin hydroaminoalkylation with a simple tertiary amine is hitherto very limited. In this study, density functional theory was applied to investigate the hydroaminoalkylation of olefins with tertiary amines, catalyzed by a series of homoleptic tris(benzyl) scandium complexes. It is found that the catalytic performance can be improved via substitution of electron-withdrawing groups and modifying ligand frameworks to reduce their steric hindrance. In addition, the potential applications of scandium catalysts in the α-C(sp3)–H alkylation of various heteroatom-containing (P, As, O, S, and Se) substrates were explored. The results suggest that alkyl sulfides and selenides are promising substrates to undergo α-C(sp3)–H addition to olefins. Importantly, the effects of ligand backbone and substituent on catalytic ...