An organocatalytic enantioselective Friedel-Crafts reaction of benzoxathiazine 2,2-dioxides with pyrroles has been developed. Chiral phosphoric acids are enanantioselective catalysts for Friedel-Crafts reaction affording the corresponding pyrrole-3-sulfamidates in good yields and with high enantioselectivities (up to 95% ee) for a broad range of functional groups and substitution patterns.