Development of Synthetic Reactions Using New Types of Lewix Acid Catalysts

1.以三氟甲磺酸和三氟甲磺酸为催化剂，成功地进行了苯和未活化苯如氯苯、氟苯的催化Friedel-Crafts酰化反应。芳香族和脂肪族羧酸酰氯在此条件下均能顺利反应，得到相应的芳香酮，产率较高.为了寻找在水中稳定的刘易斯酸催化剂，在Mukaiyama羟醛缩合反应（醛与甲硅烷基烯醇醚的羟醛缩合反应）中筛选了第1-15族元素的金属氯化物和一些高氯酸盐和三氟甲烷磺酸盐（三氟甲磺酸盐）。结果表明，基于Fe（II）、Cu（II）、Zn（II）、Cd（II）、Pb（II）以及稀土（Sc（III）、Y（III）、Ln（III））的金属化合物在水中是稳定的且活性的。这些元素（阳离子）在水中的催化活性与取代内球水配体（水）的水合常数和交换速率常数之间的关系 ...更多信息 r交换速率常数（WERC）），并且无一例外地具有pKh值从4.3至10.08和WERC大于3.2 × 10^6 M^ sec^的金属化合物<-1><-1>在羟醛缩合反应中给出了令人满意的产率。高分子负载催化剂的开发是有机合成研究的重要课题之一。特别是在向清洁和环境友好的化学工艺的发展中。我们开发了一种前所未有的聚合物支载的刘易斯酸--微胶囊化的三氟甲磺酸钪（Scandiuminflate）（MC Sc（OTf）_3）。这种将催化剂固定在聚合物上的新方法是基于聚合物的物理吸附和聚合物苯环上的π电子与刘易斯酸的空轨道之间的电子相互作用。扫描电子显微镜（SEM）显微照片显示MC Sc（OTf）_3的小胶囊相互粘附，钪能谱（EDX）分析表明，Sc（OTf）_3分布在聚合物表面。初步动力学研究表明，MC Sc（OTf）_3的活化能力比单体Sc（OTf）_3强上级。该催化剂制备简单，活性高。该催化剂具有可回收、可重复使用等优点，已成功应用于许多有用的碳-碳成键反应。少

1.Catalytic Friedel-Crafts acylation of benzene and unactivated benzenes such as chlorobenzene and fluorobenzene has been successfully carried out using hafnium (IV) inflate and trifluoromethanesulfonic acid as catalysts. Both aromatic and aliphatic carboxylic acid chlorides reacted smoothly under the conditions to afford the corresponding aromatic ketones in good yields.2. Metal chlorides and some perchlorates and trifluoromethanesulfonates (triflates) of group 1-15 elements were screened in the Mukaiyama aldol reaction (an aldol reaction of an aldehyde with a silyl enol ether) for the purpose of finding Lewis acid catalysts stable in water. It was shown that metal compounds based on Fe(II), Cu(II), Zn(II), Cd(II), Pb(II) as well as the rare earths (Sc(III), Y(III), Ln(III)) were stable and active in water. Correlation between catalytic activity of these elements (cations) in water and hydration constants and exchange rate constants for substitution of inner-sphere water ligands (wate … More r exchange rate constant (WERC)) were found, and without exception metal compounds, which have both pKh values from 4.3 to 10.08 and WERC greater than 3.2x10^6 M^<-1> sec^<-1>, gave satisfactory yields in the aldol reaction.3. Development of polymer-supported catalysts is one of the most important tasks in organic synthesis. especially in the move towards clean and environmentally friendly chemical processes. We have developed an unprecedented polymer-supported Lewis acid, a microencapsulated scandium trifluoromethanesulfonate (scandium inflate) (MC Sc(OTf)_3). This new method for immobilizing a catalyst onto a polymer is based both on physical envelopment by the polymer and on electronic interaction between pi electrons of benzene rings of the polymer and a vacant orbital of the Lewis acid.A scanning electron microscopy (SEM) micrograph revealed that small capsules of MC Sc(OTf)_3 adhered to each other, and it was also shown by scandium energy dispersive X-ray (EDX) mapping that Sc(OTf)_3 was located all over the polymer surface. One of the most remarkable points is that the activating ability of MC Sc(OTf)_3 was shown to be superior to monomeric Sc(OTf)_3 by preliminary kinetic studies. The catalyst was readily prepared and maintained high activity. Moreover, it was recoverable and reusable, and was successfully applied to many useful carbon-carbon bond-forming reactions. Less