3-Silylated Cyclohexa-1,4-dienes as Surrogates for Gaseous and Harmful Hydrosilanes in Lewis-Acid Catalysis

3-硅烷化环六-1,4-二烯作为路易斯酸催化中气态和有害氢硅烷的替代品

• 批准号: 255836950
• 负责人: Professor Dr. Martin Oestreich
• 金额: --
• 依托单位: Institut für Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/255836950?language=en
• 关键词: Silylated; Cyclohexa; dienes; Surrogates; Gaseous

The ability of the commercially available Lewis acid B(C6F5)3 to activate Si-H bonds under mild reaction conditions has led to a number of synthetically useful applications since its discovery by Piers and co-workers. Our laboratory recently disclosed for the first time that the same strong Lewis acid is able to activate a bisallylic C-H bond in 3-silylated cyclohexa-1,4-dienes, thereby catalyzing the release of hydrosilanes with concomitant formation of benzene. This procedure is particularly attractive for the generation of otherwise gaseous, highly flammable and/or harmful hydrosilanes. The readily available 3-silylated cyclohexa-1,4-dienes are easy-to-handle liquids and represent hydrosilane surrogates. The combination of the B(C6F5)3-catalyzed silane release and subsequent Si-H bond activation then paved the way to the development of an unprecedented ionic transfer hydrosilylation of alkenes. We plan to elaborate our new methodology further and expand its application in Lewis-acid catalysis based on these fundamental findings. The major goal will be the identification of suitable transfer reagent/boron Lewis acid combinations for the release and transfer of functionalized silanes.

自Piers及其同事发现以来，可商购的刘易斯酸B（C6 F5）3在温和反应条件下活化Si-H键的能力已经导致了许多合成上有用的应用。我们的实验室最近首次公开了相同的强刘易斯酸能够活化3-甲硅烷基化的环己-1，4-二烯中的双烯丙基C-H键，从而催化氢硅烷的释放并伴随苯的形成。该方法对于生成另外的气态、高度易燃和/或有害的氢硅烷特别有吸引力。容易获得的3-甲硅烷基化环己-1，4-二烯是易于处理的液体，并且代表氢硅烷替代物。B（C6 F5）3-催化的硅烷释放和随后的Si-H键活化的组合然后为烯烃的前所未有的离子转移氢化硅烷化的发展铺平了道路。我们计划进一步阐述我们的新方法，并扩大其应用在路易斯酸催化的基础上，这些基本的发现。主要目标将是确定合适的转移试剂/硼刘易斯酸组合的释放和转移的官能化硅烷。

项目成果

Formal SiH4 chemistry using stable and easy-to-handle surrogates

• DOI: 10.1038/nchem.2329
• 发表时间: 2015-08
• 期刊: Nature Chemistry
• 影响因子: 21.8
• 作者: Antoine Simonneau;M. Oestreich

Direct and Transfer Hydrosilylation Reactions Catalyzed by Fully or Partially Fluorinated Triarylboranes: A Systematic Study

• DOI: 10.1021/om501284a
• 发表时间: 2015-02-23
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Keess, Sebastian;Simonneau, Antoine;Oestreich, Martin
• 通讯作者: Oestreich, Martin