Base‐Mediated Synthesis of Sulfur‐Substituted Imides using <i>N</i> ‐(acyloxy)‐Tetrachlorophthalimides/Anhydrides and Alkyl Isothiouronium Salts

Imides have a vast presence in pharmaceuticals and natural products, and their synthesis generally relies on the utility of the disagreeable strong oxidants. Herein, we report an oxidant‐free protocol that combines N ‐(acyloxy)‐tetrachlorophthalimides, derived from abundant carboxylic acids, and acid anhydrides with isothiouronium salts. Crucial to this protocol is the provision of access to sulfur‐substituted imides, which were previously limited to sulfur‐ β ‐allyl‐substituted imides and the use of undesirable free thiols. To this end, this developed protocol provides a scalable and functional group‐tolerant reactivity with product yields of up to 96% under mild reaction conditions.