Copper‐Catalyzed Enantioselective C1,N‐Dipolar (3 + 2) Cycloadditions of 2‐Aminoallyl Cations with Indoles

2-Aminoallyl cations are versatile 1,3-dipoles that could potentially be used for diverse (3+n) cycloaddition reactions. Despite some preliminary studies, the asymmetric catalytic transformation of these species is still underdeveloped. We herein report a binuclear copper-catalyzed generation of 2-aminoallyl cations from ethynyl methylene cyclic carbamates and their enantioselective (3+2) cycloaddition reaction with indoles to construct chiral pyrroloindolines. This transformation features a novel C1,N-dipolar reactivity for 2-aminoallyl cations.