Facile Synthesis of S-Fused Multi-Membered Polycyclic Heterocycles:A Construction Strategy towards Thermally Stable Thiepine Derivatives
作者机构：Lab of Advanced MaterialsState Key Laboratory of Molecular Engineering of PolymersFudan UniversityShanghai 200438China
出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)
年 卷 期：2023年第41卷第1期
页 面：13-20页
核心收录：
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
基 金：supported by the National Key Research and Development Program of China(2018YFA0209401) the National Natural Science Foundation of China(22171053,21733003) the Natural Science Foundation of Shanghai(21zR1409600)
主 题：Sulfur heterocycles Fused-ring systems Thiepine Thiopyran Aromaticity
摘 要：S-fused heterocycles have become popular building blocks to construct functional polycyclic *** contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal ***,a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure ***,the dilithium intermediates are ex-cluded,which facilitates the fusion on the thiepine ring with different S-heterocycles,including thiophene and thiopyran ***,a S-fused multi-membered polycyclic compound simultaneously involving thiophen,thiopyran,and thiepine rings has been successfully ***,nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics,***,the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit,which is attributed to the enhancements of the activation energies for the S-extrusion reactions,as revealed by density functional theory ***,our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles,but also furnish a novel construction strategy towards thermally stable thiepine derivatives.
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