摘要：手性环戊烯酮是许多活性天然产物和多种药物合成的关键中间体。多年来，化学家们采用了不同的方法合成该片段，而其中最为突出的便是4-羟基环戊烯酮。该环戊烯酮片段用途广泛，可作为抗菌活性物质、前列腺素药物中间体等。但与此同时，该片段极易消旋化，且自身不稳定，在一定的酸碱条件下易发生逆羟醛缩合反应。本实验以糠醛作为反应原料经过加成反应制得重排反应底物，在反应中，共使用五种不同的试剂对其进行反应，并在反应过程中注重对于反应温度的选取，其反应产率为80-90%之间。再将其经过Piancatelli 重排反应得到具有不同取代基团的手性环戊烯酮分子片段。该步为整个实验的关键步骤，由于重排反应机理的复杂性，所得到的产率并不高，一般在30-50%之间。所得分子再经过酶动力学拆分、Michael加成以及消除反应等，可得到更具药用价值的其他药物中间体。并在此基础上，从产品纯度、产品质量、操作条件、成本、反应时间、绿色化学等角度对实验进行综合性分析，最大程度优化反应路线。31971
毕业论文关键字： 重排反应、手性分子、4-羟基环戊烯酮
The application of Piancatelli rearrangement in the Synthesis of medicine intermediate
Abstract：Chiral cyclopentenone is the key intermediate for a lot of active natural products and a variety of drug synthesis. For many years, chemists have used different methods to synthesize this molecule. One of the most prominent molecule is 4-hydroxycyclopentenone. This molecule has a wide range of uses. It can be used as antimicrobial active substance; pharmaceutical intermediates of prostaglandin and so on. At the same time, this molecule is easy to be racemized. And it is unstable. Under some acid-base conditions, it is easy to produce reverse aldol reaction. In this experiment, we use furfural as raw material, and through additive reaction to get the raw material of rearrangement reaction. In this experiment, we use five different reagents to make this reaction, and we pat emphasis on the choice of reaction temperature, and the productivity is about 80-90%. And the through Piancatelli rearrangement reaction, we can get different chiral cyclopentenone molecules. This is the most important step in all the experiments. And because of the complicated mechanism, the productivity of the reaction is  not very high, only about 30-50%. And then through enzymatic kinetic resolution; Michael addition reaction and elimination reaction, we can get another pharmaceutical intermediates with higher medicinal value. Based on this foundation, we make a comprehensive analysis about product purity; product quantity; operating conditions; cost; reaction time and green chemistry. We will try our best to optimized the reaction routes.
Key Words：rearrangement reaction； chiral molecule；4-hydroxycyclopentenone
目录
1 绪论    1
1.1 课题背景与意义    1
1.2 Piancatelli重排反应的简介    1
1.2.1 Piancatelli重排反应产物的相关化学信息    2
1.2.2 Piancatelli重排反应的应用价值    2
1.2.3 Piancatelli重排反应方法    2
1.3 本课题主要研究内容    3
1.3.1 Piancatelli重排反应路线的研究现状    3
1.3.2 Piancatelli重排反应路线优化    4
1.4 合成路线拟定    4
2 实验部分    7
2.1 实验试剂和仪器    7
2.1.1 实验试剂    7
2.1.2 实验仪器    7
2.1.3 试剂的物理常数    8
2.2 Piancatelli重排反应机理    8
2.3 4-羟基环戊烯酮的制备    10
2.3.1 以甲基氯化镁为原料制备4-羟基环戊烯酮分子    10 Piancatelli重排反应在药物中间体合成中的应用:http://www.youerw.com/yixue/lunwen_28333.html