Organophosphine-Mediated Skeletal Editing Synthesis of Benzo[e][1,3]thiazine-2,4(3H)-diones via Curtius Rearrangement
Shanhong Yang1, Kunwei Guo1, Huizhi Hu1
1Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, China.
Abstract:
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.
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