Development of Efficient Vinylation and Ethynylation Reactions

高效乙烯基化和乙炔化反应的发展

基本信息

批准号：
13557193
负责人：
YAMAGUCHI Masahiko
金额：
$ 9.09万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13557193/
关键词：
vinylation catalysis phenol enolate ethynylation transition metal sulfonic acid disulfide ホスフィン

项目摘要

Vinylation and ethynylation are fundamental transformations in organic synthesis, which provide synthetically important intermediates for functionalized polymers and biologically interesting heterocyclic compounds. Conventional methods employed stepwise transformation, and were not efficient in terms of economical and environmental demands. This project is aimed to develop novel and efficient methods to vinylate and ethynylate C-H bonds of organic molecules.Previously, we developed phenol o-vinylation reaction with ethyne in the presence of Sn Cl_4 and Bu_3N. The method required use of excess tin reagent, and a catalytic method was developed. In the presence of SnCl_4 and BuLi, o-substituted phenols can he vinylated with silylacetylene with the turnover number close to 10. Enolate vinylation reaction using GaCl_3 was also examined, and the method was found to be applicable not only to ketones but also to thioesters and malonates. It is notable that thermodynamically unstable vinylmalonates can be prepared. As for the stereochemistry, the reactions exhibit an equatorial selectivity in the vinylation of cyclohexanone derivatives.Ethynylation reactions were developed using addition/elimination reaction of organogallium compounds to chloroacetylene. Silyl enolates can be ethynylated at the α-position in the presence of GaCl_3, and phenols at the 0-position. Catalytic processes using GaCl_3 was developed.A novel catalyst system was developed employing a transition metal and sulfonic acid, which allows addition of trianylphosphines to allenes and 1,3-dienes.The present project provided a series of vinylation and ethynylation reactions of organic compounds, which may find a broad application in the synthesis of functionally interesting compounds.

乙烯化和乙基化是有机合成中的基本转化，它们为功能化聚合物和生物学有趣的异环化合物提供了合成重要的中间体。常规方法采用了逐步转化，在经济和环境需求方面不高。该项目的目的是开发有机分子的乙烯基和乙基乙基乙烯酸乙二醇化和乙基乙基键的新颖方法。在存在Sn Cl_4和BU_3N的情况下，我们与Ethyne开发了与乙烯的苯酚O-乙烯化反应。该方法需要使用过量的TIN试剂，并开发了一种催化方法。在SNCL_4和Buli存在的情况下，可以用甲莲乙酰基烯醇将O取代的苯酚乙醇乙醇乙烯乙烯，周转数接近10。还检查了使用GACL_3的烯醇化反应，并且发现该方法不仅适用于酮，而且适用于酮酸盐和thioesters和Thioesters和Thioesters and Malonates。值得注意的是，可以制备热力学上不稳定的乙烯基甲硅酸盐。至于立体化学，这种反应在环己酮衍生物的乙烯基化中表现出了等效性的选择性。使用有机金化合物对氯乙烯的加法/消除反应，开发了乙烯烯反应。在存在GACL_3的情况下，可以在α-位上以乙二烯烯烯丙基化和0位的苯酚进行乙醇。开发了使用GACL_3的催化过程。采用过渡金属和磺酸开发了一种新型的催化剂系统，允许将三氨基膦添加到艾伦和1,3-二烯中。目前的项目提供了一系列的vinyllation和乙基甲基甲基化的反应，在有机化合物中可以找到广泛的化合物，该反应可在合成中具有功能上有趣的配置。