A Programmable Cut-and-Sew Strategy for Trisulfide Transfer in the Synthesis of Cyclic Architectures

While sulfides and disulfides have been extensively studied, trisulfides─particularly in cyclic form─have attracted comparatively limited attention. Progress in this area has been limited largely by the intrinsic lability of the S-S-S unit, which complicates controlled synthesis and restricts access to these motifs. In this study, we describe a metal-free programmable trisulfurating strategy that constructs cyclic trisulfides through a sequential "cut-and-sew" process. The reaction relies on controlled reactivity at both termini of a trisulfide unit, enabling successive C-SSS bond cleavage and formation within a single molecular framework, operating under mild conditions with only a base as the additive. The method enables the synthesis of six- to nine-membered cyclic trisulfides, late-stage modification of complex bioactive molecules, and access to linear trisulfides under mild conditions. Several products display antibacterial activity against plant pathogens. These results establish a general framework for trisulfide synthesis and suggest opportunities for extending related strategies to higher-order chalcogen motifs.