N-甲磺酰芳基肼的Suzuki交叉偶联及乳酸催化的四氢喹啉合成的Povarov反应研究

发布时间：2018-02-16 13:51

本文关键词： Suzuki交叉偶联反应 N’-对甲磺酰基芳基肼 Povarov反应乳酸四氢喹啉　出处：《江西师范大学》2016年硕士论文　论文类型：学位论文

【摘要】：联苯类化合物广泛存在于天然产物、现代药物分子、农用化学品以及功能材料中,因此发展新型及有效的方法来合成这些骨架对有机化学来说是一项非常重要的工作。Suzuki-Miyaura交叉偶联反应是合成联苯类化合物最可靠的方法之一,针对以前有人发表过N-对甲苯磺酰基芳基肼作为亲电试剂应用于Suzuki交叉偶联反应生成联芳基化合物,考虑到原子经济性的问题,我们采用了N-甲磺酰基芳基肼来代替上述亲电试剂。四氢喹啉骨架是一种很重要的有机结构单元,被发现存在于许多生物活性天然产物和人工合成的医药制剂中,四氢喹啉衍生物广泛应用于生物、医药、药理学,例如:缓激肽抑制剂、抗过敏药制剂、抗肿瘤制剂、NMDA受体抑制剂等都是四氢喹啉衍生物。在已知的合成方法中,Povar ov反应是合成四氢喹啉衍生物最温和、最实用的方法之一。以前有人已经用一系列催化剂如:三氟乙酸、BPC、三氯化钆、镧系化合物、手性磷酸化合物、硫脲等作为有效催化剂来催化该反应合成取代的四氢喹啉衍生物,本文则采用了易得且便宜的乳酸来催化此类反应合成取代的四氢喹啉衍生物。本文分为两部分,第一部分是我们发展了用N-甲磺酰基芳基肼作为前体化合物和芳基硼酸的交叉偶联反应,可以合成重要的联苯类化合物。该反应以5mol%钯盐作催化剂,碳酸钾作为碱,以中等到优秀的收率快速得到一系列的联苯类化合物。本文第二部分是我们发展了用乳酸作为催化剂来催化Povarov反应以合成自然界中重要的四氢喹啉衍生物。该反应以0.5当量的乳酸作催化剂,可得到中等至优良收率的一系列四氢喹啉衍生物。
[Abstract]:Biphenyls are widely found in natural products, modern drug molecules, agrochemicals and functional materials. Therefore, the development of new and effective methods to synthesize these skeletons is a very important work for organic chemistry. Suzuki-Miyaura cross-coupling reaction is one of the most reliable methods for the synthesis of biphenyl compounds. N- p-toluenesulfonyl aryl hydrazine has been used as an electrophilic reagent in Suzuki cross-coupling reactions to produce biaryl compounds, considering the economy of atoms. N- methanesulfonyl aryl hydrazine was used to replace the electrophilic reagents mentioned above. Tetrahydroquinoline skeleton is a very important organic structural unit and has been found in many bioactive natural products and synthetic pharmaceutical preparations. Tetrahydroquinoline derivatives are widely used in biology, medicine, pharmacology, such as bradykinin inhibitors, antiallergic preparations, Antitumor agents such as NMDA receptor inhibitors are tetrahydroquinoline derivatives. Povarov reaction is the most moderate in the synthesis of tetrahydroquinoline derivatives. One of the most practical methods. A series of catalysts such as BPC, gadolinium trichloride, lanthanide compounds, chiral phosphoric acid compounds and thiourea have been used as effective catalysts for the synthesis of substituted tetrahydroquinoline derivatives. In this paper, the readily available and inexpensive lactic acid was used to catalyze the synthesis of substituted tetrahydroquinoline derivatives. In the first part, we developed a cross-coupling reaction between N-methanesulfonyl aryl hydrazine and aryl boric acid to synthesize important biphenyl compounds, which were catalyzed by 5mol% palladium salt and base by potassium carbonate. A series of biphenyls were rapidly obtained in medium to excellent yields. In the second part of this paper, we developed the catalytic reaction of Povarov using lactic acid as catalyst to synthesize important tetrahydroquinoline derivatives in nature. A 0.5 equivalent amount of lactic acid shall be used as a catalyst, A series of tetrahydroquinoline derivatives with moderate to excellent yield can be obtained.
【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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