{"title":"一锅催化 C-S 偶联锌配合物的机械化学级联合成","authors":"Daming Feng, Xiujia Hao, Zhenduo Fei, Peng Huang, Fang Guo","doi":"10.1021/acs.organomet.4c00200","DOIUrl":null,"url":null,"abstract":"The mechanochemical approach to transition metal catalysis offers a number of advantages, including a reduction in solvent usage and an acceleration of reaction times. This study elucidates a one-pot, two-step cascade catalytic synthesis enabled by mechanochemistry, which integrates the synthesis of bidentate zinc complexes and their application in carbon–sulfur coupling reactions. The zinc complexes were systematically modified by altering the halogen atoms attached to the metal center, utilizing the reduced Schiff base ligand <i>N,N’</i>-diphenylethylenediamine, which significantly influenced the catalytic efficiency. Under optimal conditions, a wide range of thioether products were synthesized, demonstrating broad applicability across various substrates. The mechanistic insights were enhanced through the execution of free radical trapping experiments and analysis of reaction intermediates, revealing an S<sub>N</sub>2 substitution mechanism in the formation of carbon–sulfur bond. Furthermore, the methodology adheres to green chemistry principles, as evidenced by the favorable green chemistry metrics obtained, indicating a sustainable and eco-friendly protocol for practical use.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"50 1","pages":""},"PeriodicalIF":2.9000,"publicationDate":"2024-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mechanochemical Cascade Synthesis of Zinc Complexes for Catalytic C–S Coupling in One-Pot\",\"authors\":\"Daming Feng, Xiujia Hao, Zhenduo Fei, Peng Huang, Fang Guo\",\"doi\":\"10.1021/acs.organomet.4c00200\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The mechanochemical approach to transition metal catalysis offers a number of advantages, including a reduction in solvent usage and an acceleration of reaction times. This study elucidates a one-pot, two-step cascade catalytic synthesis enabled by mechanochemistry, which integrates the synthesis of bidentate zinc complexes and their application in carbon–sulfur coupling reactions. The zinc complexes were systematically modified by altering the halogen atoms attached to the metal center, utilizing the reduced Schiff base ligand <i>N,N’</i>-diphenylethylenediamine, which significantly influenced the catalytic efficiency. Under optimal conditions, a wide range of thioether products were synthesized, demonstrating broad applicability across various substrates. The mechanistic insights were enhanced through the execution of free radical trapping experiments and analysis of reaction intermediates, revealing an S<sub>N</sub>2 substitution mechanism in the formation of carbon–sulfur bond. Furthermore, the methodology adheres to green chemistry principles, as evidenced by the favorable green chemistry metrics obtained, indicating a sustainable and eco-friendly protocol for practical use.\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"50 1\",\"pages\":\"\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-07-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00200\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00200","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Mechanochemical Cascade Synthesis of Zinc Complexes for Catalytic C–S Coupling in One-Pot
The mechanochemical approach to transition metal catalysis offers a number of advantages, including a reduction in solvent usage and an acceleration of reaction times. This study elucidates a one-pot, two-step cascade catalytic synthesis enabled by mechanochemistry, which integrates the synthesis of bidentate zinc complexes and their application in carbon–sulfur coupling reactions. The zinc complexes were systematically modified by altering the halogen atoms attached to the metal center, utilizing the reduced Schiff base ligand N,N’-diphenylethylenediamine, which significantly influenced the catalytic efficiency. Under optimal conditions, a wide range of thioether products were synthesized, demonstrating broad applicability across various substrates. The mechanistic insights were enhanced through the execution of free radical trapping experiments and analysis of reaction intermediates, revealing an SN2 substitution mechanism in the formation of carbon–sulfur bond. Furthermore, the methodology adheres to green chemistry principles, as evidenced by the favorable green chemistry metrics obtained, indicating a sustainable and eco-friendly protocol for practical use.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.