Asymmetric Transfer Hydrogenation of 1,3‐Disubstituted 3,4‐Dihydroisoquinolines via Dynamic Kinetic Resolution

A facile and efficient asymmetric transfer hydrogenation of racemic 1,3‐disubstituted 3,4‐dihydroisoquinolines has been developed via a dynamic kinetic resolution process. This method affords 1,3‐disubstituted tetrahydroisoquinolines in high yields with excellent stereoselectivities (up to 99% yield, >20:1 dr, 98% ee) in aqueous phase (CH 3 CN/H 2 O, 1:1), and performs comparably in an organic solvent (DCE). Compared with conventional protocols, this approach avoids the use of high‐pressure hydrogen gas and features mild reaction conditions, operational simplicity, excellent functional group tolerance, and applicability to late‐stage drug functionalization. Mechanistic insights were obtained through nonlinear effect studies, kinetic studies, control experiments, and DFT calculations.