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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.

乙烯基化和乙炔化是有机合成中的基本转化，为功能化聚合物和具有生物学意义的杂环化合物提供合成上重要的中间体。传统方法采用逐步转化，在经济和环境要求方面效率不高。该项目旨在开发新颖有效的方法来乙烯基化和乙炔化有机分子的C-H键。之前，我们开发了在Sn Cl_4和Bu_3N存在下苯酚与乙炔的邻乙烯基化反应。该方法需要使用过量的锡试剂，因此开发了催化方法。在SnCl_4和BuLi存在下，邻位取代苯酚可以用甲硅烷基乙炔进行乙烯基化，转化率接近10。还考察了GaCl_3的烯醇化乙烯基化反应，发现该方法不仅适用于酮类，还适用于硫酯类和丙二酸酯类。值得注意的是，可以制备热力学不稳定的乙烯基丙二酸酯。在立体化学方面，该反应在环己酮衍生物的乙烯基化反应中表现出赤道选择性。利用有机镓化合物与氯乙炔的加成/消除反应发展了乙炔化反应。在 GaCl_3 存在下，甲硅烷基烯醇化物可以在 α 位被乙炔化，苯酚则可以在 0 位被乙炔化。开发了使用GaCl_3的催化工艺。采用过渡金属和磺酸开发了一种新型催化剂体系，可以将三苯膦加成到丙二烯和1,3-二烯上。本项目提供了一系列有机化合物的乙烯基化和乙炔化反应，可能在功能有趣的化合物的合成中得到广泛的应用。