电化学氧化合成四取代烯烃以及安息香醚的研究.pdfVIP

摘 要 电化学催化合成有机分子近年来备受关注。由于其可持续性和环境友好的内 在特征，通过电化学氧化直接功能化 C-H 键或简单的底物已成为热门话题。在 该领域中已有很多相关报道，利用简单高效的电化学氧化方法，通过简单的乙腈 3 的 C(sp )-H 键活化引入氰基以及直接氧化炔烃得到目标分子是一个简单、便捷 的方式。 本论文主要包括以下两个部分的研究： 3 1.第一部分发展一种在无过渡金属的条件下简单高效的实现乙腈的 C(sp )- H 键活化，进而和硫酚类化合物直接转化为含氰基的四取代烯烃的反应。该反应 合成了多种广泛存在于天然产物、药物分子的含氰基四取代烯烃类化合物，并成 功实现了克级规模的实验。 2.第二部分发展了一种直接电化学氧化炔烃合成苯偶姻醚的方法，这种转化 可以在温和的反应条件下进行，不需要外部氧化剂和过渡金属催化剂。初步的机 理研究表明，产物中羰基氧来源于水。 关键词：电化学氧化；四取代烯烃；乙腈；炔烃；苯偶姻醚 I Abstract Electrochemical catalytic synthesis of organic molecules has attracted much attention in recent years. Due to its inherent characteristics of sustainability and environmental friendliness, direct functionalization of C-H bonds or simple substrates by electrochemical oxidation has become a hot topic. There have been many relevant reports in this field. It is a simple and convenient way to obtain the target molecule through simple activation of C(sp3)-H bond of acetonitrile and introduction of cyanogroup and direct oxidation of alkynes. This paper mainly includes the following two parts of the research: (1) The first part develops a simple and efficient reaction of acetonitrile C(sp3)-H bond activation in the absence of transition metals and the direct conversion of thiophenols to cyanogen-containing tetra-substituted alkenes. In this reaction, a variety of cyanotetra-substituted alkenes containing cyanotetra-substituted alkenes, which are widely existed in natural products and drug molecules, were synthesized, and the experiments in gram scale were successfully carried out. (2) In the second part, a direct electrochemical synthesis of benzoin ether from alkynes was developed. This transformation