Photocatalytic Synthesis of Unprotected Sulfonimidamides and Their Application in Photochemical Nitrene Transfer Reactions

Abstract The selective incorporation of nitrogen into organic molecules remains a central challenge in modern synthetic chemistry, particularly when aiming to access complex, functionalized scaffolds under mild and sustainable conditions. In this report, we describe a photocatalytic method that employs hydroxylamine‐derived nitrene precursors and unprotected sulfinamides under mild conditions, enabling efficient nitrene transfer without the need for stoichiometric amounts of an oxidant. The resulting unprotected sulfonimidamides serve not only as target compounds but also as versatile intermediates for further nitrene‐transfer reactions, affording complex sulfur–nitrogen‐rich frameworks. Mechanistic studies support a photoinduced single‐electron transfer process involving a reactant complex between the photocatalyst and nitrene precursor. This work establishes a general and modular platform for accessing challenging architectures based on sulfonimidamides, expanding the toolkit for late‐stage functionalization and heteroatom‐rich molecule construction.