68887-17-2Relevant academic research and scientific papers
Photogeneration of thiyl radicals using metal-halide perovskite for highly efficient synthesis of thioethers
Liu, Xin,Bai, Rong,Guo, Zhifen,Che, Yan,Guo, Chunyi,Xing, Hongzhu
, (2021/11/01)
Recently, the use of metal-halide perovskite (MHP) for photoinduced organics transformation has attracted much attention. We report herein the development of photoinduced thiol-ene reaction using inorganic MHP of CsPbBr3 nanocrystal that is visible light-responsive, easy-to-prepare, and cost-effective. Under blue light-emitting diode (LED), a series of thiol substrates are demonstrated to be highly efficient reaction partners to couple with alkenes tolerated with various functional groups, affording diverse thioethers containing C–S bonds. The CsPbBr3-mediated thiol-ene reaction is characterized by high efficiency, broad substrate applicability, excellent yields, and mild conditions. Mechanism investigation shows that the visible light-excited CsPbBr3 induces the generation of thiyl radicals via hole oxidation to initiate the reaction, followed by redox neutral pathway and/or chain transfer pathway to accomplish thiol–olefin coupling. It is notable that CsPbBr3 exhibits advanced thiol-ene performance than that using MHP analogs and others. The work presents a new exploration of MHP-mediated transformation and shows great potential of MHPs for radical chemistry.
Photoactive Metal-Organic Frameworks for the Selective Synthesis of Thioethers: Coupled with Phosphine to Modulate Thiyl Radical Generation
Guo, Zhifen,Liu, Xin,Bai, Rong,Che, Yan,Chi, Yanhong,Guo, Chunyi,Xing, Hongzhu
supporting information, p. 8672 - 8681 (2021/06/28)
Metal-organic framework (MOF) materials are intriguing photocatalysts to trigger radical-mediated chemical transformations. We report herein the synthesis and characterization of a series of isomorphic MOFs which show a novel structure, wide visible-light absorption, high chemical stability, and specific redox potential. The prepared MOFs were explored for the photoinduced single-electron oxidation of thiol compounds, generating reactive thiyl radicals to afford thioethers via a convenient thiol-olefin reaction. Importantly, we provide a widely applicable strategy by combing a photoactive MOF with phosphine to modulate the generation of thiyl radical in the reaction, thereby producing a single product of the thioether without the formation of a disulfide byproduct due to the dimerization of thiyl radicals. The photocatalytic reaction takes advantage of this strategy, showing great generality where tens of thiols and olefins have been examined as coupling partners. In addition, the strategy has also been demonstrated to be effective for the reactions catalyzed by other MOFs. Mechanism studies reveal that the selective synthesis of C-S products relies on a synergy between the photoinduced generation of a thiyl radical over the MOF and the in situ cleavage of S-S bond into a S-H bond by phosphine. It is notable that the synthesized MOFs show advanced performance in comparison with classical MOFs. The work not only provides a series of novel MOF photocatalysts that are capable of photoinduced thiol-olefin coupling but also indicates the great potential of MOFs for photochemical transformations mediated by reactive radicals.
Development of enantioselective polyclonal antibodies to detect styrene oxide protein adducts
Shen, Shuijie,Zhang, Fan,Zeng, Su,Tian, Ye,Chai, Xiaojuan,Gee, Shirley,Hammock, Bruce D.,Zheng, Jiang
experimental part, p. 2668 - 2677 (2010/04/04)
Styrene has been reported to be pneumotoxic and hepatotoxic in humans and animals. Styrene oxide, a major reactive metabolite of styrene, has been found to form covalent binding with proteins, such as albumin and hemoglobin. Styrene oxide has two optical
