Pd-catalyzed intermolecular Si–O formation via Si–C activation

作     者：Shuang Liu Yu-Shu Chen Yichen Wu Peng Wang 

作者机构：State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic ChemistryUniversity of Chinese Academy of SciencesShanghai 200032China School of Chemistry and Materials ScienceHangzhou Institute for Advanced StudyUniversity of Chinese Academy of SciencesHangzhou 310024China College of Material Chemistry and Chemical EngineeringKey Laboratory of Organosilicon Chemistryand Material Technology of Ministry of EducationHangzhou Normal UniversityHangzhou 311121China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第8期

页      面：2661-2669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 R&D Program of China (2023YFF0723900) the National Natural Science Foundation of China (22371293, 22171277, 22101291, 21821002) the Program of Shanghai Academic/Technology Research Leader(23XD1424500) the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0610000) Shanghai Institute of Organic Chemistry (SIOC) State Key Laboratory of Organometallic Chemistry for financial support 

主　　题：Si–O formation Si–C activation palladium silacyclobutane silanol silyl ether 

摘      要：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.