Organophosphine-Mediated Skeletal Editing Synthesis of Benzo[e][1,3]thiazine-2,4(3 H )-diones via Curtius Rearrangement

作者：S. Y. Yang, K. H. Guo, Huizhi Hu, Xiaobing Liu, Yao Zhou, Shengzhou Jin · 发表于：The Journal of Organic Chemistry · 年份：2025 · DOI：10.1021/acs.joc.5c02348 · 被引用次数：7 · 研究领域：Catalytic C–H Functionalization Methods、Synthesis and Catalytic Reactions、Click Chemistry and Applications

An organophosphine-promoted skeletal reorganization of benzo[c][1,2]dithiol-3-ones to forge benzo[e][1,3]thiazine-2,4(3H)-diones is demonstrated herein. This cascade reaction involves S–S bond cleavage followed by formal [4 + 2] cycloaddition of benzo[c][1,2]dithiol-3-ones and isocyanates, which are generated in situ through the Curtius rearrangement of acyl azides or dioxazolones beyond the formation of N-acyl nitrenes. The newly developed S to C–N exchange strategy endows the efficient assembly of diverse benzo[e][1,3]thiazine-2,4-diones under mild conditions, which avoids transition metals and inert gas protection, featuring a simple reaction setup to achieve decent yields while allowing for both late-stage diversification and practical scalability.