Catalytic Enantioselective Aminopalladation–Heck Cascade

Abstract Domino processes initiated by intramolecular nucleopalladation of alkynes have been developed into powerful synthetic tools for the synthesis of functionalized heterocycles. However, a catalytic enantioselective version of this class of reactions remains scarce. We report herein that reaction of 2‐alkynylanilines with prochiral cyclopentenes in the presence of a catalytic amount of Pd(OAc) 2 , a chiral bidentate pyrox ligand and O 2 as terminal oxidant affords the structurally diverse indole‐cyclopentene conjugates bearing two stereocenters in a highly diastereo‐ and enantio‐selective manner. One of the products is converted to a heavily functionalized tetracyclic indolinone derivative.