Aluminum(III) complexes derived from aminotriphenolate ligands are shown to be excellent catalysts for the formation of cyclic sulfites from a range of (functionalized) terminal and internal epoxides, and ex situ generated sulfur dioxide. The developed catalytic protocol is characterized by its operational simplicity, wide scope in epoxide reaction partners, good to excellent isolated yields and mild reaction conditions 50–70 °C, p(SO2) <1 bar]. The synthetic potential of these cyclic sulfites in organic synthesis is demonstrated in the preparation of N‐substituted aziridines through a three‐step protocol.
