School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, China.
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062, China.
Nat Commun. 2021 Dec 15;12(1):7298. doi: 10.1038/s41467-021-27167-x.
Tetraarylethylenes exhibit intriguing photophysical properties and sulfur atom frequently play a vital role in organic photoelectric materials and biologically active compounds. Tetrasubstituted vinyl sulfides, which include both sulfur atom and tetrasubstituted alkenes motifs, might be a suitable skeleton for the discovery of the new material molecules and drug with unique functions and properties. However, how to modular synthesis these kinds of compounds is still challenging. Herein, a chemo- and stereo-selective Rh(II)-catalyzed [1,4]-acyl rearrangements of α-diazo carbonyl compounds and thioesters has been developed, providing a modular strategy to a library of 63 tetrasubstituted vinyl sulfides. In this transformation, the yield is up to 95% and the turnover number is up to 3650. The mechanism of this reaction is investigated by combining experiments and density functional theory calculation. Moreover, the "aggregation-induced emission" effect of tetrasubstituted vinyl sulfides were also investigated, which might useful in functional material, biological imaging and chemicalnsing via structural modification.
四芳基乙烯具有有趣的光物理性质，而硫原子在有机光电材料和生物活性化合物中经常起着至关重要的作用。四取代乙烯基硫醚，同时包含硫原子和四取代烯烃部分，可能是发现具有独特功能和性质的新材料分子和药物的合适骨架。然而，如何进行模块化合成这些化合物仍然具有挑战性。在此，开发了一种铑（II）催化的α-重氮羰基化合物和硫代酯的化学和立体选择性[1,4]-酰基重排反应，为 63 个四取代乙烯基硫醚库提供了一种模块化策略。在该转化中，产率高达 95%，周转数高达 3650。通过实验和密度泛函理论计算相结合，研究了该反应的机理。此外，还研究了四取代乙烯基硫醚的“聚集诱导发射”效应，通过结构修饰，可能对功能材料、生物成像和化学传感有用。
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