Metal‐Free Chemoselective Amide Bond Cleavage for the Synthesis of <i>N</i> ‐Acyl Sulfoximines in Batch and Flow

Amides and sulfoximines are pivotal structural motifs in pharmaceuticals and agrochemicals; however, sustainable and direct methods for their incorporation remain underdeveloped. Herein, a metal‐ and additive‐free protocol is presented for the efficient synthesis of N ‐acyl sulfoximines via selective NC bond cleavage of amides, utilizing bench‐stable N‐ acyl saccharin as an acylating agent for NH‐sulfoximines. This transformation proceeds under mild conditions using green solvents and exhibits a broad substrate scope encompassing natural products and drug derivatives. Notably, the method is compatible with both batch and continuous‐flow platforms, achieving a significant reduction in reaction time from 24 h to 15 min. The process offers high yields, excellent functional group tolerance, and gram‐scale scalability. Furthermore, the recovery of recyclable saccharin enhances atom economy and minimizes waste generation.