Ag‐Catalyzed Cyclization‐Intermolecular Sulfinyl Group Transfer Cascade Reactions Enabling Enantioselective Synthesis of 4‐Sulfinylisoquinolines

N‐Sulfinylimines derived from ortho‐alkynylbenzaldehydes were efficiently converted into the corresponding 4‐sulfinylisoquinolines in good to excellent yields. The reaction proceeds via cyclization followed by intermolecular migration of the sulfinyl group from the nitrogen atom to the silver‐bound carbon of the resulting cyclized vinylsilver intermediate with the aid of either a counteranion or a nucleophilic species. Moreover, the Ag‐catalyzed reaction in the presence of quinidine acetate as a chiral nucleophilic cocatalyst yielded chiral isoquinolines with high enantioselectivities through a dynamic kinetic asymmetric transformation (DYKAT).