【作者】 方勇；

【导师】 罗云飞；

【作者基本信息】 合肥工业大学 ， 化学工程与技术， 2021， 硕士

【摘要】 铁系化合物作为催化剂在有机合成中的应用是极具吸引力的,因为其价格远远低于经常使用的贵金属催化剂,近年许多过渡金属和稀土金属的价格大幅上涨,使得寻找更为便宜的替代物已迫在眉睫;此外各种铁化合物广泛存在于各种生物体中,因而许多铁化合物对生物体具有相对较低的毒性,这对包括制药工业、食品工业和化妆品工业在内的许多现代化工合成制造业具有重要价值。异喹啉类生物碱由于其高效的生物活性受到了众多化学合成与医药学领域的关注,许多相关产品已在临床医学上广泛使用。对其的合成尤其是结构复杂的衍生物的合成往往存在合成步骤多、反应原料和催化剂昂贵、副产物多等问题。而烯丙基硼试剂可以与羰基化合物或是亚胺经过一步简单反应获得多手性中心的结构复杂的手性醇及胺,在喹啉及衍生物合成中有着重要的应用前景,以铁系化合物作为催化剂,使用烯丙基硼试剂实现异喹啉的衍生物合成既满足绿色化学要求又能实现简单步骤和较低成本的目的。本文分为两个部分,分别介绍了几种烯丙基硼试剂和几种异喹啉合成方法以及烯丙基硼试剂对异喹啉的加成研究。第一部分:以各种取代基苯乙胺为起始原料制备一系列的二氢异喹啉,合成出苯环上有各种不同取代基的1-甲基-3,4-二氢异喹啉以及不同α位取代的3,4-二氢异喹啉。另外,以几种烯醇为原料经过几步反应制备几种不同烷基取代基的烯丙基氟硼酸钾盐以及手性烯丙基氟硼酸钾盐等烯丙基硼试剂。第二部分:以几种3,4-二氢异喹啉和烯丙基硼试剂为底物研究基于铁催化的二氢异喹啉的烯丙基化的反应,通过一系列实验获得适合的基于铁化合物的催化体系和反应条件,研究3,4-二氢异喹啉和烯丙基硼试剂在目标催化体系中的应用范围以及具体反应情况,探究该目标反应的规律,基于此反应获得一系列新的化合物并获得其准确结构。更多还原

【Abstract】 The application of iron-based compounds as catalysts in organic synthesis is extremely attractive because their prices are far lower than the frequently used precious metal catalysts.In recent years,the prices of many transition metals and rare earth metals have risen sharply,making it possible to find cheaper alternatives.It is imminent;in addition,various iron compounds are widely present in various organisms,so many iron compounds have relatively low toxicity to organisms,which is important for many modern synthetic manufacturing industries including the pharmaceutical industry,the food industry and the cosmetics industry.Has important value.The wide biological activities of isoquinoline alkaloids have attracted the attention of many chemical synthesis and medicine neighborhoods,and many related products have been widely used in clinical practice.Its synthesis,especially the synthesis of complex derivatives,often has problems such as many synthesis steps,expensive reaction materials and catalysts,and many by-products.The allyl boron reagent can react with carbonyl compounds or imines to obtain chiral alcohols and amines with complex structures with multiple chiral centers through a simple one-step reaction.It has important potential applications in the synthesis of quinolines and derivatives.The compound is used as a catalyst,and the allyl boron reagent is used to realize the synthesis of isoquinoline derivatives not only to meet the requirements of green chemistry,but also to achieve the purpose of simple steps and lower costs.This article is divided into two parts,introducing several allyl boron reagents and several isoquinoline synthesis methods,as well as the addition of allyl boron reagents to isoquinoline.Part Ⅰ: Prepare a series of dihydroisoquinolines with various substituent phenethylamines as starting materials,and prepare corresponding allyl boron reagents through several steps of reactions with several enols as raw materials.Synthesize 1-methyl-3,4-dihydroisoquinolines with various substituents on the benzene ring and other types of 3,4-dihydroisoquinolines,as well as several allyls with different alkyl substituents Allyl boron reagents such as potassium fluoroborate and chiral potassium fluoroborate.Part Ⅱ: Using several 3,4-dihydroisoquinoline and allyl boron reagents as substrates to study the iron-catalyzed allylation reaction of dihydroisoquinoline,a series of experiments were carried out to obtain suitable Based on the catalytic system and reaction conditions of the iron compound,study the application range of 3,4-dihydroisoquinoline and allyl boron reagent in the target catalytic system and the specific reaction conditions,explore the law of the target reaction,and based on this reaction Obtain a series of new compounds to obtain their precise structures.更多还原