銥催化氧化吲哚的合成及鉗型環(huán)鉑有機(jī)化合物在含硫氨基酸識(shí)別中的應(yīng)用
發(fā)布時(shí)間:2018-11-10 16:09
【摘要】:氧化吲哚衍生物擁有重要的生物活性或藥用價(jià)值,因此,如何快速高效地合成氧化吲哚衍生物引起了合成化學(xué)家的重視。在過渡金屬的作用下,基于導(dǎo)向基團(tuán)誘導(dǎo)的高選擇性C-H鍵的直接官能團(tuán)化反應(yīng)具有良好的化學(xué)和區(qū)域選擇性、原子以及反應(yīng)步驟經(jīng)濟(jì)性。我們利用胺基作為導(dǎo)向基團(tuán),實(shí)現(xiàn)了吲哚2-位的碳?xì)滏I的直接轉(zhuǎn)化,高效合成了氧化吲哚衍生物。另一方面,含硫氨基酸在生物體內(nèi)重要的作用,高效識(shí)別含硫氨基酸一直都是熱門研究領(lǐng)域,我們利用鉗形環(huán)鉑化合物擁有的自組裝和熒光發(fā)射的性質(zhì),實(shí)現(xiàn)了對(duì)含硫氨基酸的可視識(shí)別。本論文第一章介紹合成氧化吲哚的研究現(xiàn)狀,從鈀催化、銅催化、其它金屬催化方面論述氧化吲哚的合成方法;同時(shí),列舉了硫醇熒光探針的發(fā)展現(xiàn)狀,介紹了基于硫醇對(duì)邁克爾受體的加成反應(yīng)、硫醇和醛的成環(huán)反應(yīng)、硫醇參與的過硫鍵斷裂反應(yīng)、硫醇與金屬絡(luò)合反應(yīng)來設(shè)計(jì)的熒光探針。論文第二章發(fā)展了吲哚乙烯胺類化合物在銥(~Ⅲ)和過氧化氫異丙苯的作用下的催化氧化反應(yīng),高選擇性地實(shí)現(xiàn)了吲哚2-位的碳?xì)滏I官能團(tuán)化,高效合成3-烯基-2-氧化吲哚衍生物;诔醪降姆磻(yīng)機(jī)理研究,提出了可能的反應(yīng)機(jī)理。論文第三章研究了鉗型環(huán)鉑配合物的凝聚性能和選擇性對(duì)含硫氨基酸的響應(yīng)性能,實(shí)現(xiàn)了對(duì)含硫氨基酸的可視識(shí)別。合成了一系列具有新型結(jié)構(gòu)的鉗型環(huán)鉑配合物,并經(jīng)過了充分的表征。
[Abstract]:Oxyindole derivatives have important biological activity or medicinal value, so how to synthesize them quickly and efficiently has attracted the attention of synthetic chemists. Under the action of transition metal, the direct functionalization of C-H bond with high selectivity induced by guided group has good chemical and regional selectivity, atom and step economy. The direct conversion of the indole-2-site hydrocarbon bond was realized by using the amino group as the guiding group, and the oxindole-derivative was synthesized efficiently. On the other hand, the important role of sulfur-containing amino acids in organisms, the efficient identification of sulfur-containing amino acids has been a hot research field. Visual recognition of sulfur-containing amino acids was realized. In the first chapter of this paper, the research status of the synthesis of oxindoles is introduced, and the synthesis methods of oxindoles are discussed from the aspects of palladium catalysis, copper catalysis and other metal catalysis. At the same time, the development of mercaptan fluorescence probe is listed. Based on the addition reaction of mercaptan to Michael receptor, the cyclization reaction between mercaptan and aldehydes, and the hypersulfur bond breaking reaction in which mercaptan is involved, A fluorescent probe designed by the complexation of mercaptan with metal. In chapter 2, the catalytic oxidation of indole ethylamine compounds under the action of iridium (鈪,
本文編號(hào):2322916
[Abstract]:Oxyindole derivatives have important biological activity or medicinal value, so how to synthesize them quickly and efficiently has attracted the attention of synthetic chemists. Under the action of transition metal, the direct functionalization of C-H bond with high selectivity induced by guided group has good chemical and regional selectivity, atom and step economy. The direct conversion of the indole-2-site hydrocarbon bond was realized by using the amino group as the guiding group, and the oxindole-derivative was synthesized efficiently. On the other hand, the important role of sulfur-containing amino acids in organisms, the efficient identification of sulfur-containing amino acids has been a hot research field. Visual recognition of sulfur-containing amino acids was realized. In the first chapter of this paper, the research status of the synthesis of oxindoles is introduced, and the synthesis methods of oxindoles are discussed from the aspects of palladium catalysis, copper catalysis and other metal catalysis. At the same time, the development of mercaptan fluorescence probe is listed. Based on the addition reaction of mercaptan to Michael receptor, the cyclization reaction between mercaptan and aldehydes, and the hypersulfur bond breaking reaction in which mercaptan is involved, A fluorescent probe designed by the complexation of mercaptan with metal. In chapter 2, the catalytic oxidation of indole ethylamine compounds under the action of iridium (鈪,
本文編號(hào):2322916
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