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 O2 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.