We developed a highly enantioselective Friedel-Crafts reaction of indoles, 4,7-dihydroindole and pyrrole with α-amidosulfones as sensitive imine surrogates using a cooperative cation-binding catalyst. In this new catalytic protocol heteroaromatic and aliphatic substrates as well as α-imino ethyl glyoxylate also afforded the desired products with excellent yields and ees. Thus, this method enables the catalytic synthesis of biologically interesting natural products and pharmaceutically relevant chiral Friedel-Crafts indole/pyrrole adducts. Due to the conformational stability of the transition state at high temperature, all the proposed intermediates were identified by the ESI-MS analysis. Furthermore, the key to this successful catalytic activity is the cation-binding catalysis in a densely confined chiral space in situ formed by the incorporation of potassium salt. Like enzymes in a confined space, thus enhancing the reactivity and efficiently transferring the stereochemical information.