【作者】 张彪；

【导师】 戴建军； 许华建； 方红新；

【作者基本信息】 合肥工业大学 ， 制药工程（专业学位）， 2022， 硕士

【摘要】 烯丙基芳烃是构建有效分子的具有价值的试剂,同时也是许多具有生物活性的天然产物中的重要结构基序,由于其特别的结构,展现出了有趣的药理和物理性质。三取代烯烃广泛分布在有价值的分子中,比如天然产物、药物和有机材料,它是有机化学合成中的通用组成部分。另外,二苯乙烯衍生物因其具有治疗和预防作用而一直处于药物研究和开发的前沿,例如抗雌激素药物他莫昔芬、抗氧化剂白藜芦醇;它们还经常出现在染料前体、荧光增白剂、荧光粉和闪烁体中。迄今为止,绝大多数方法是通过单芳基烯烃或炔烃和各种芳基试剂反应来合成烯丙基芳烃和三取代烯烃,这些方法中有的选择性很差,有的底物兼容性不好。在此基础上,我们考虑避免使用芳基烯烃和炔烃,而使用丙炔醇和芳基试剂通过一锅法生成具有双芳基的烯烃结构。该论文的研究就是通过简单易得的丙炔醇和芳基硼酸为原料合成具有双芳基的产物。经过之前实验的积累和努力,我们发现了钯催化的丙炔醇的双芳基化反应。发现该反应初期,得到两种互为同分异构体的双芳基化产物,产物之一是烯丙基化芳烃,之二是三取代烯烃,并由此衍生了钯催化丙炔醇生成烯丙基芳烃和三取代烯烃的双芳基化反应,并进行反应条件进一步优化。在第二章中,发现使用2.5当量苯硼酸,会得到具有高度选择性的烯丙基芳烃产物,使用5当量苯硼酸,会得到高度选择性的三取代烯烃产物。该种方法相对于传统方式来说,路径简便且高效,而且可以通过改变芳基硼酸的用量得到相应的双芳基化产物。更多还原

【Abstract】 Allylarenes are valuable reagents for the construction of effective molecules and are also important structural motifs in many biologically active natural products,exhibiting interesting pharmacological and physical properties due to their special structures.Trisubstituted alkenes are widely distributed in valuable molecules,such as natural products,pharmaceuticals,and organic materials,and are versatile building blocks in organic chemical synthesis.In addition,stilbene derivatives have been at the forefront of drug research and development due to their therapeutic and preventive effects,such as the anti-estrogen drug tamoxifen,the antioxidant resveratrol;they are also frequently found in dye precursors,In optical brighteners,phosphors and scintillators.So far,the vast majority of methods are to synthesize allylarenes and trisubstituted alkenes by reacting monoarylalkenes or alkynes with various aryl reagents,some of these methods have poor selectivity and some are substrate compatible.not good.On this basis,we consider avoiding the use of aryl alkenes and alkynes and instead use propynyl alcohols and aryl reagents to generate alkene structures with bisaryl groups through a one-pot method.The research of this paper is to synthesize the products with double aryl groups by using simple and readily available propynyl alcohol and aryl boronic acid as raw materials.After the accumulation and efforts of previous experiments,we discovered the palladium-catalyzed bisarylation of propynyl alcohols.It was found that in the early stage of the reaction,two bis-arylation products that were isomers of each other were obtained.One of the products was an allylated aromatic hydrocarbon,and the other was a tri-substituted alkene,and palladium-catalyzed propynyl alcohol was derived from this.Bi-arylation of allyl arenes and trisubstituted olefins,and further optimized the reaction conditions.In Chapter 2,it was found that using 2.5 equivalents of phenylboronic acid gave highly selective allylic aromatic products,and using 5 equivalents of phenylboronic acid gave highly selective trisubstituted olefin products.Compared with the traditional method,the method is simple and efficient,and the corresponding bis-arylation product can be obtained by changing the amount of arylboronic acid.更多还原