{"title":"Frustrated Lewis Pair-Promoted Organocatalytic Transformation of Hydrosilanes into Silanols with Water Oxidant","authors":"Fuyu Xie, Sutao Zhang, Mo Yang, Jianghua He, Shuhua Li, Yuetao Zhang","doi":"10.1021/jacs.4c07818","DOIUrl":null,"url":null,"abstract":"Owing to their unique properties, the silanols have attracted intense attention but remain challenging to prepare from the organocatalytic oxidation of hydrosilanes using H<sub>2</sub>O as a green oxidant. Herein, we employ a frustrated Lewis pair (FLP) to successfully suppress the formation of undesired siloxanes and produce silanols in high to excellent yields in the presence of H<sub>2</sub>O. Mechanistic studies suggest that the reaction is initiated with the activation of FLP by H<sub>2</sub>O rather than by silanes and goes through a concerted S<sub>N</sub>2 mechanism. More importantly, the combination of the FLP-catalyzed oxidation of hydrosilanes with B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-catalyzed dehydrogenation enables us to realize the precise synthesis of sequence-controlled oligosiloxanes. This method exhibits a broad substrate scope and can be easily scaled up, thus exhibiting promising application potentials in the precision synthesis of silicon-containing polymer materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c07818","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Owing to their unique properties, the silanols have attracted intense attention but remain challenging to prepare from the organocatalytic oxidation of hydrosilanes using H2O as a green oxidant. Herein, we employ a frustrated Lewis pair (FLP) to successfully suppress the formation of undesired siloxanes and produce silanols in high to excellent yields in the presence of H2O. Mechanistic studies suggest that the reaction is initiated with the activation of FLP by H2O rather than by silanes and goes through a concerted SN2 mechanism. More importantly, the combination of the FLP-catalyzed oxidation of hydrosilanes with B(C6F5)3-catalyzed dehydrogenation enables us to realize the precise synthesis of sequence-controlled oligosiloxanes. This method exhibits a broad substrate scope and can be easily scaled up, thus exhibiting promising application potentials in the precision synthesis of silicon-containing polymer materials.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.