A copper‐catalyzed [3+2] cylcoaddition/ alkenyl C−N coupling tandem reaction was demonstrated. It provided a method for the formation of triazolopiperidine skeletons.

Chiral o-aminobenzylamines are synthons for many chiral ligands and catalysts which have been widely used in asymmetric synthesis. Herein, we report a highly efficient and stereoselective addition of Grignard reagent to o-aminosulfinylimine for a range of o-aminosulfinylimines in good yields with good to excellent diastereoselectivity.