{"title":"通过 Si-C 活化实现 Pd 催化分子间 Si-O 形成","authors":"Shuang Liu, Yu-Shu Chen, Yichen Wu, Peng Wang","doi":"10.1007/s11426-024-1951-0","DOIUrl":null,"url":null,"abstract":"<p>The development of efficient Si–O bond formation reaction with 100% atom-economy, excellent functional group tolerance, and broad scope under mild conditions is highly desired due to the prevalence of silanol, silyl ether, and their derivatives in synthetic chemistry and materials science. Here, we have realized the Pd-catalyzed Si–O formation reaction <i>via</i> a Si–C activation approach with 100% atom-economy by employing silacyclobutanes (SCBs) and various hydroxy-containing substrates, including water, alcohols, phenols, and silanols. This protocol features a broad substrate scope, remarkable functional compatibility and mild conditions, providing a series of silanols, silyl ethers in high efficiency. Notably, this protocol could also be used for selective protection of hydroxy functionalities, and for the access of a class of novel polymers containing Si–O main chain. Preliminary mechanistic studies unveiled that this reaction underwent a Pd-catalyzed concerted ring-opening mechanism.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":null,"pages":null},"PeriodicalIF":10.4000,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Pd-catalyzed intermolecular Si–O formation via Si–C activation\",\"authors\":\"Shuang Liu, Yu-Shu Chen, Yichen Wu, Peng Wang\",\"doi\":\"10.1007/s11426-024-1951-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The development of efficient Si–O bond formation reaction with 100% atom-economy, excellent functional group tolerance, and broad scope under mild conditions is highly desired due to the prevalence of silanol, silyl ether, and their derivatives in synthetic chemistry and materials science. Here, we have realized the Pd-catalyzed Si–O formation reaction <i>via</i> a Si–C activation approach with 100% atom-economy by employing silacyclobutanes (SCBs) and various hydroxy-containing substrates, including water, alcohols, phenols, and silanols. This protocol features a broad substrate scope, remarkable functional compatibility and mild conditions, providing a series of silanols, silyl ethers in high efficiency. Notably, this protocol could also be used for selective protection of hydroxy functionalities, and for the access of a class of novel polymers containing Si–O main chain. Preliminary mechanistic studies unveiled that this reaction underwent a Pd-catalyzed concerted ring-opening mechanism.</p>\",\"PeriodicalId\":772,\"journal\":{\"name\":\"Science China Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.4000,\"publicationDate\":\"2024-06-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science China Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1007/s11426-024-1951-0\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science China Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1007/s11426-024-1951-0","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Pd-catalyzed intermolecular Si–O formation via Si–C activation
The development of efficient Si–O bond formation reaction with 100% atom-economy, excellent functional group tolerance, and broad scope under mild conditions is highly desired due to the prevalence of silanol, silyl ether, and their derivatives in synthetic chemistry and materials science. Here, we have realized the Pd-catalyzed Si–O formation reaction via a Si–C activation approach with 100% atom-economy by employing silacyclobutanes (SCBs) and various hydroxy-containing substrates, including water, alcohols, phenols, and silanols. This protocol features a broad substrate scope, remarkable functional compatibility and mild conditions, providing a series of silanols, silyl ethers in high efficiency. Notably, this protocol could also be used for selective protection of hydroxy functionalities, and for the access of a class of novel polymers containing Si–O main chain. Preliminary mechanistic studies unveiled that this reaction underwent a Pd-catalyzed concerted ring-opening mechanism.
期刊介绍:
Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field.
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