Development of Efficient Vinylation and Ethynylation Reactions

乙烯基化和乙基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的合成提供了重要的中间体。传统的方法采用逐步转化，在经济和环境要求方面效率不高。本项目旨在开发新的、有效的方法来乙烯化和乙基化有机分子的C-H键。在此之前，我们在Cl_4和Bu_3N的存在下进行了苯酚-乙烯基化反应。该方法需要使用多余的锡试剂，并开发了一种催化方法。在SnCl_4和BuLi存在下，o-取代苯酚与硅乙炔发生乙烯化反应，周转率接近10。研究了用GaCl_3进行烯醇酸乙烯化反应，发现该方法不仅适用于酮类，而且适用于硫酯和丙二酸酯。值得注意的是，可以制备热力学不稳定的丙二酸乙烯酯。在立体化学方面，环己酮衍生物的乙烯化反应具有赤道选择性。利用有机镓化合物与氯乙炔的加成/消除反应，建立了乙基化反应。在GaCl_3和0位酚的存在下，硅烯醇酯可以在α-位置发生乙基化。开发了以GaCl_3为催化剂的催化工艺。采用过渡金属和磺酸，开发了一种新的催化剂体系，可以将三苯基膦添加到烯和1,3-二烯中。本项目提供了一系列有机化合物的乙烯基化和乙基化反应，在合成功能感兴趣的化合物方面具有广泛的应用前景。

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.