不对称sulfa-Michael反应以及重氮膦酸酯参与的不对称环化-Mannich串联反应

发布时间：2018-05-16 15:43

本文选题：不对称催化 + sulfa-Michael反应　；参考：《西南大学》2017年硕士论文

【摘要】：碳-杂键的形成在有机合成反应中具有非常重要的作用,这吸引了有机化学家的研究兴趣,并提出了许多高效合成碳-杂键的方法。由于有机硫化合物和有机氮化合物普遍存在于自然界和各种生物系统,特别是手性的天然产物和药物分子当中,因此碳-硫(C-S)与碳-氮(C-N)键的形成在碳杂键的合成中占据重要地位。其中,不对称催化作为合成手性化合物的重要手段被广泛用于合成含杂原子的手性化合物。本论文从以下两部分阐述合成含杂原子手性化合物的研究工作:第一部分:设计了苯硫酚与硝基烯的不对称sulfa-Michael反应,通过多功能硫脲催化实现了手性硫醚类化合物的高效合成。反应具有条件温和、催化剂负载量低(1 mol%)、收率(99%)和对映选择性高(99%ee)等优点。该反应不仅适应各类取代的芳基硫酚、苄硫醇以及脂肪族硫醇,而且对单取代、多取代硝基烯都表现出强的兼容性。反应可以在较低催化剂负载量(0.05 mol%)的情况下放大到克级。第二部分:实现了重氮膦酸酯与邻炔基芳醛、伯胺发生的不对称环化-Mannich串联反应,合成了手性1,2-二氢异喹啉类化合物。首先设计合成了各种3,3'-取代的手性联萘以及螺环磷酸,然后与碳酸银原位生成手性磷酸银催化该串联反应。通过对各类催化剂的筛选,取得了中等的收率和较优的选择性。
[Abstract]:The formation of carbon-hetero-bonds plays a very important role in organic synthesis reactions, which attracts the research interests of organic chemists and puts forward many efficient methods for the synthesis of carbon-hetero-bonds. Because organic sulfur compounds and organic nitrogen compounds are ubiquitous in nature and various biological systems, especially chiral natural products and drug molecules, Therefore, the formation of C-S and C-N bonds plays an important role in the synthesis of carbon heterodyne bonds. Among them, asymmetric catalysis is widely used in the synthesis of chiral compounds containing heteroatoms as an important means of synthesis of chiral compounds. In this paper, the synthesis of chiral compounds containing heteroatom is described in the following two parts: the first part: the asymmetric sulfa-Michael reaction of phenythiophenol with nitroene was designed, and the high efficiency synthesis of chiral thioether compounds was realized by multifunctional thiourea catalysis. The reaction has the advantages of mild conditions, low catalyst loading (1 mol / L, yield of 99%) and high enantioselectivity (99). This reaction not only adapts to all kinds of substituted aryl thiophenols, benzyl mercaptans and aliphatic mercaptans, but also has strong compatibility for monosubstituted and polysubstituted nitroenes. The reaction can be amplified to g level under the condition of lower catalyst loading (0.05 mol / L). In the second part, the asymmetric cyclization Mannich series reaction of diazo phosphonate with o-alkynyl aromatic aldehydes and primary amines has been realized, and chiral 1H _ 2-dihydroisoquinoline compounds have been synthesized. Various kinds of chiral binaphthalene and spirocyclic phosphoric acid were designed and synthesized firstly, and then the chiral silver phosphate was synthesized in situ with silver carbonate to catalyze the series reaction. Through the screening of various catalysts, a moderate yield and a better selectivity were obtained.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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