Development of One Step Synthesis of Vinylsilanes from Olefins Catalyzed by Transition Metal

过渡金属催化烯烃一步合成乙烯基硅烷的研究进展

基本信息

批准号：
02555175
负责人：
MURAI Shinji
金额：
$ 4.67万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02555175/
关键词：
Vinylsilane Olefin Iron carbonyl Wilkinson complex 鉄カルボニル触媒遷移金属ヒドロシラン

项目摘要

Vinylsilanes are one of important monomers for the preparation of functinalized materials such as membranes for oxygen enrichment as well as versatile synthetic intermediates in organic synthesis. Conventional method for the preparation of vinylsilanes has been the reaction of acetylenes with hydrosilanes. However, this is not practical method for the production of industrial chemicals, except for the case of the reaction of unsubstituted acetylene with trichlorosilane.The objective of this research project is to develop and establish the highly efficient synthetic method for vinylsilanes from olefins by using new catalytic reactions developed by our group, that is dehydrogenative silylation of olefins with a hydrosilane.1. It was found that a suitable combination of the structures of the olefin, hydrosilane, and catalyst is essential for dehydrogenative silylation to take place. For example, M_3(CO)_<12>(M = Fe, Ru, Os)showed high catalytic activity for the reaction of styrene with triethylsilane. Among them, Fe_3(CO)_<12> showed 100% selectivity, no alkylsilane being obtained as a byproduct. The similar reaction of 1, 5-dienes with triethylsilane was effectively catalyzed by Rh(PPh_3)_3Cl. -2. Ligand effect was examined for ruthenium-catalyzed reaction of styrene with triethoxysilane. Information about the reaction mechanism was collected.In conclusion, it was found that a suitable combination of olefin-catalyst is essential for dehydrogenative silylation to take place. Some practical methods for the preparation of vinylsilanes are established.

乙烯基硅烷是制备功能化材料的重要单体之一，例如有机合成中的氧气富集以及多功能合成中间体。制备乙烯基烷烷的常规方法是乙酰基烯与氢硅烷的反应。但是，这不是生产工业化学物质的实际方法，除了未取代的乙炔与三氯硅烷的反应外，该研究项目的目的是通过使用我们的小组开发的新型催化反应来开发和建立从烯烃中的乙烯基硅烷的高效合成方法，该反应是脱脂型硅化作用的a lifeane limelation a a a a a a a a a a i olefinal olefillical olefineLation olefinal olefillical olefillical olefillical olefilliel olefilfins。发现烯烃，氢硅烷和催化剂的结构合适的结合对于脱氢作用是至关重要的。例如，M_3（CO）_ <12>（M = Fe，Ru，OS）显示出苯乙烯与三乙基硅烷反应的高催化活性。其中，Fe_3（CO）_ <12>显示100％选择性，没有作为副产品获得的烷基硅烷。 RH（PPH_3）_3Cl有效地催化了1，5-二烯与三乙基硅烷的相似反应。 -2。检查了配体效应的苯乙烯与三乙氧基硅烷的弦烯催化反应。结论，发现烯烃 - 催化剂的合适组合对于脱氢作用至关重要。建立了一些用于乙烯基硅烷制备的实际方法。