本文選題：手性氮膦配體 + 不對(duì)稱催化��； 參考：《寧波大學(xué)》2017年碩士論文

【摘要】：過渡金屬催化反應(yīng)在有機(jī)合成領(lǐng)域中有著極其廣泛的應(yīng)用,通過該類型反應(yīng)可以構(gòu)建碳?xì)�、碳碳、碳氮、碳氧、碳硫等鍵,可以合成多種復(fù)雜的活性藥物中間體和手性有機(jī)分子。在過渡金屬催化反應(yīng)中,手性氮膦配體的應(yīng)用一直是研究的重點(diǎn)。設(shè)計(jì)合成出一種結(jié)構(gòu)新穎、容易制備、高活性的氮膦配體,且能與過渡金屬螯合來催化反應(yīng)時(shí)具備高選擇性,仍然是一個(gè)具有挑戰(zhàn)性的難題。本論文針對(duì)這一難題,展開了研究工作,合成了一類以天然樟腦為主要骨架的手性氮膦配體,并研究了其在不對(duì)稱催化烯丙基化反應(yīng)和Suzuki偶聯(lián)反應(yīng)中的應(yīng)用。我們以商業(yè)化的天然樟腦為手性源,并運(yùn)用模塊化的概念,通過簡(jiǎn)單的修飾與偶聯(lián)合成了一類新型的手性氮膦配體。該手性氮膦配體保留了天然樟腦的剛性骨架結(jié)構(gòu),而且原料易得、易于合成,在空氣中穩(wěn)定。同時(shí)我們研究了其與過渡金屬鈀螯合,不對(duì)稱催化烯丙基化反應(yīng)和Suzuki偶聯(lián)反應(yīng)。研究表明,由天然樟腦衍生的新型席夫堿類化合物是一類高效的氮膦配體,能夠有效催化吲哚類的不對(duì)稱烯丙基化反應(yīng),表現(xiàn)出卓越的催化性能,以良好的產(chǎn)率(高達(dá)92%yield)和優(yōu)秀的對(duì)映選擇性(高達(dá)98%ee)得到多種手性產(chǎn)物。手性氮膦配體在催化大位阻Suzuki偶聯(lián)反應(yīng)中,表現(xiàn)出優(yōu)越的催化性能,最高以97%yield得到偶聯(lián)產(chǎn)物。說明了剛性的天然樟腦骨架結(jié)構(gòu)在該類配體中起著重要的作用。
[Abstract]:Transition metal catalytic reactions are widely used in the field of organic synthesis, through which bonds such as carbon, carbon, carbon and nitrogen, carbon and oxygen, carbon and sulfur can be constructed. Many complex active drug intermediates and chiral organic molecules can be synthesized. The application of chiral nitrogen-phosphine ligands in transition metal catalytic reactions has been the focus of research. It is still a challenging problem to design and synthesize a novel, easily prepared, highly active nitrophosphine ligand with high selectivity for catalytic reaction with transition metal chelation. In order to solve this problem, a class of chiral nitrophosphine ligands with natural camphor as the main skeleton were synthesized and their applications in asymmetric allylation and Suzuki coupling reactions were studied. Using commercial natural camphor as chiral source and using the concept of modularization, a novel chiral nitrophosphine ligands were synthesized by simple modification and coupling. The chiral nitrophosphine ligands retain the rigid skeleton structure of natural camphor, and the raw materials are easy to be obtained, easy to synthesize and stable in air. At the same time, we studied their chelation with transition metal palladium, asymmetric allylation and Suzuki coupling reaction. The results show that the novel Schiff base compounds derived from natural camphor are a class of highly efficient nitrophosphine ligands, which can effectively catalyze the asymmetric allylation of indole and exhibit excellent catalytic performance. A variety of chiral products were obtained with good yield (up to 92 yield) and excellent enantioselectivity (up to 98). Chiral nitrophosphine ligands showed excellent catalytic performance in the large steric barrier Suzuki coupling reaction, and the coupling products were obtained by 97%yield. It is concluded that rigid natural camphor skeleton plays an important role in this kind of ligand.
【學(xué)位授予單位】：寧波大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25

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本文編號(hào)：1865213