关键词： 普瑞巴林   动力学拆分   不对称合成  

摘要： 普瑞巴林为Pfizer公司上市的新型γ-氨基丁酸(GABA)受体拮抗剂,临床用于治疗癫痫、焦虑和由脊髓损伤、外伤或多发性硬化症等引起的中枢神经疼痛,应用较为广泛,近年来文献报道合成方法较多.对普瑞巴林的合成方法进行了总结和概述,其中重点介绍了动力学拆分、去对称化反应、不对称氢化和不对称Michael加成等不对称合成方法.

关键词： 吡咯烷   氮杂糖   糖苷酶抑制剂   合成等效体   氮杂半缩醛  

摘要： 报道了多用途的吡咯烷类氮杂糖中间体6的不对称合成.起始原料(2R,3R,4S)-2-苄氧甲基-3,4-二苄氧基-5-氧代吡咯烷-1-羧酸叔丁酯(8)由手性合成砌块酒石酸酰亚胺7按照先前本实验室报道的方法经4步得到.活化的酰胺8经乙烯基加成、立体选择性还原、环化、氧化断裂双键成醛以及还原醛成醇等步骤得到了氮杂糖中间体(2R,3R,4R,5R)-2-羟甲基-3,4-二苄氧基-5-苄氧甲基吡咯烷-1-羧酸叔丁酯(6).从活化的酰胺8出发,经过5步反应,立体选择性地合成了氮杂糖中间体6,总产率46%.中间体6可用于多个吡咯烷类氮杂糖的合成.

关键词： L-亮氨酸   手性酰胺   不对称合成  

摘要： 本文以L-亮氨酸为手性源与甲基丙烯酰氯合成了一种新的酰胺类手性可聚合单体。对其红外、核磁进行了表征,并测定其在不同溶剂中的比旋光度值。

摘要： The tetrahydroquinolines structural unit is found in a number of natural products that exhibit a variety of biological activities including anti-allergic, anti-inflammatory and antitumour. As a result there is significant interest in their synthesis. This PhD thesis describes the work undertaken in the development of a new synthetic route that can be applied to the asymmetric synthesis of structurally diverse tetrahydroquinolines. The introductory chapter outlines the main current synthetic strategies towards tetrahydroquinolines and their application to the synthesis of some biologically interesting compounds. Chapter 2 discusses work on the total asymmetric synthesis of the Galipea alkaloids. An aza-Michael reaction was used to install the required stereochemistry. Extensive optimisation of the aza-Michael reaction resulted in high enantioselectivities, with optically pure material obtained upon recrystallisation. Various synthetic procedures were investigated for formation of the tetrahydroquinoline ring system and the remainder of the synthesis, with the Galipea alkaloids obtained from a common precursor. Work towards the formal synthesis of the Martinelline alkaloids, using the aza-Michael reaction to set the first stereocentre, is detailed in Chapter 3. A range of different α, β-unsaturated carbonyl and anilines were investigated for the aza-Michael reaction, with 85% enantioselectivity obtained on optimisation. Formation of the tetrahydroquinoline core was achieved and the installation of the second chiral centre investigated. Chapter 4 describes any miscellaneous work conducted, including preliminary investigations towards the synthesis of levonantradol. The last Chapter contains the experimental procedures and characterisation data for all the compounds synthesised during the course of this project.

关键词： 亨利反应   不对称合成   催化剂  

摘要： 在有机合成中,亨利反应是一个非常有效的构造碳碳键的反应[1],1895年,Henry首先发现了此反应[2],它主要是硝基烷烃（提供亲核试剂）与醛或者酮类（作为亲电试剂）反应生成β-硝基醇类化合物,此产物可以作为一种重要的中间原料,能用来制备多种多样有机物,特别是通过不对称亨利反应并进一步还原得到的手性β-氨基醇类化合物，

关键词： 手性诱导   配位化合物   不对称烃基化   合成  

摘要： 以([S)—BPB-Gly]N(iII)为原料,与多聚甲醛进行α-碳上的Aldol羟甲基化反应,经醋酐脱水,产物再与甲醇进行Michael亲核加成,得(S)-O-甲基-丝氨酸,其结构经1H-NMR、元素分析和旋光测定表征。

关键词： Asymmetric synthesis.   Catalysis.  

ISBN: (数字)9781118087992 ISBN: (纸本)9780470641361

摘要： This book covers advances in the methods of catalytic asymmetric synthesis and their applications. Coverage moves from new materials and technologies to homogeneous metal-free catalysts and homogeneous metal catalysts. The applications of several methodologies for the synthesis of biologically active molecules are discussed. Part I addresses recent advances in new materials and technologies such as supported catalysts, supports, self-supported catalysts, chiral ionic liquids, supercritical fluids, flow reactors and microwaves related to asymmetric catalysis. Part II covers advances and milestones in organocatalytic, enzymatic and metal-based mediated asymmetric synthesis, including applications for the synthesis of biologically active molecules. Written by leading international experts, this book consists of 16 chapters with 2000 References and illustrations of 560 schemes and figures.

关键词： 铱催化体系   不对称转移氢化   (S)-(-)-1-苯基-1-丙醇   苯丙酮   精细化工中间体  

摘要： 考察了苯丙酮在手性胺膦配体与[IrHCl2(COD)]2组成的催化体系下不对称转移氢化合成(S)-(-)-1-苯基-1-丙醇的反应,通过正交实验考察了反应温度、n(底物)∶n(铱催化剂)、n(铱催化剂)∶n(手性配体)和碱用量对反应的影响。结果表明,在异丙醇中,利用该体系催化苯丙酮反应6 h后,反应转化率可达94.5%,对映选择性(ee)达96.0%。

关键词： β-不饱和酮   不对称合成   不对称催化   Michael反应   内酰胺   胺盐   手性   分子骨架  

摘要： γ-丁内酰胺及其衍生物等分子骨架广泛存在于天然产物中．尽管此类分子骨架非常重要，金属或有机小分子催化的不对称合成中使用最多的是其烯醇硅醚衍生物，而能将最基本、最简单的α,β-不饱和-γ-丁内酰胺直接用于不对称催化、不对称合成的例子则很少．

关键词： (S)-2,2-二甲基环丙甲酰胺   重氮乙酸乙酯   异丁烯   不对称合成   手性铜配合物  

摘要： 重氮乙酸乙酯和异丁烯在手性铜配合物催化下进行环丙烷化反应,以较好的产率和光学纯度得到(S)-2,2-二甲基环丙甲酸乙酯,再经过皂化、酯化、酰胺化反应制得光学纯的标题化合物。