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  本文選題：過渡金屬催化 + 偶聯(lián)反應(yīng)　； 參考：《沈陽師范大學(xué)》2017年碩士論文

【摘要】：近年來,作為有力的合成手段,過渡金屬催化的偶聯(lián)反應(yīng)和碳氫鍵活化反應(yīng)發(fā)展迅速,含氮和含硫雜環(huán)化合物因其特殊的結(jié)構(gòu)及生物活性,對其的研究也日漸豐富。因此,利用過渡金屬催化的偶聯(lián)反應(yīng)和碳氫鍵活化反應(yīng)來實現(xiàn)含氮雜環(huán)化合物的合成與修飾受到越來越多的關(guān)注。本文在此基礎(chǔ)上對吡唑并噻嗪類衍生物、異喹啉類衍生物、含氮稠雜環(huán)化合物的合成以及吲哚啉類衍生物的修飾做了較為細致的研究,成果如下:開發(fā)了一種高效的銅催化的三組分的“一鍋兩步法”合成吡唑并噻嗪衍生物的新方法。該反應(yīng)使用廉價易得的1-(2-鹵代苯基)-3-烷基丙-2-炔-1-酮衍生物,鹽酸肼和β-二硫代甲酯為底物原料,在溫和的條件下,使用碘化亞銅作為催化劑,碳酸銫為堿,乙腈作溶劑,三組分下分為兩步一鍋就可以成功合成相對應(yīng)的吡唑并噻嗪衍生物。所得到的目標產(chǎn)物含有羰基或鹵素等具有功能性的官能團,為進一步的修飾提供了便利和可能。報道了一種高效實用的銥催化的合成異喹啉衍生物的新方法,該方法在銥催化劑的催化作用下,同時實現(xiàn)碳氫鍵活化反應(yīng)和環(huán)化反應(yīng)的串聯(lián)。反應(yīng)采用易得的苯甲酰亞胺衍生物和α-重氮羰基化合物作為原料,[Cp*IrCl2]2作催化劑,六氟銻酸銀為添加劑,甲醇作溶劑,在溫和的條件下,即可高收率制得異喹啉衍生物。該反應(yīng)對于不同的官能團都顯示出優(yōu)異的容忍性,且分離簡單,給異喹啉衍生物的合成提供了一條新的路線。開發(fā)了一種高效實用的銠催化吲哚啉C-7位胺化的新方法。該反應(yīng)采用苯并異VA唑衍生物為胺化試劑,以吲哚啉衍生物為反應(yīng)底物,[Cp*RhCl2]2為催化劑,六氟銻酸銀為添加劑,四氫呋喃為溶劑,在溫和的條件下,實現(xiàn)吲哚啉C-7位的胺化,得到相應(yīng)的目標產(chǎn)物具有氨基、羰基、醛基、鹵素或硝基等具有功能性的官能團,可以進行更深入的修飾或在藥物合成領(lǐng)域發(fā)揮作用。開發(fā)了一種簡單實用的方法,該方法以芳基唑和α-二氮羰基化合物作為底物,[Cp*RhCl2]2為催化劑,六氟銻酸銀為添加劑,四氫呋喃為溶劑,在溫和的條件下,通過Rh(III)催化的連續(xù)C-H鍵活化和環(huán)化,合成有價值的含氮稠雜環(huán)化合物。在該方案中,使用的芳基唑包括吡唑,苯并咪唑和1,2,4-三唑,并且大多數(shù)吡唑在溫和條件下都可以順利而有效地進行反應(yīng)。這為用于候選藥物篩選的多種潛在生物活性含氮稠雜環(huán)化合物的構(gòu)建提供了新的可替代方法。
[Abstract]:In recent years, as a powerful method of synthesis, transition metal-catalyzed coupling reactions and hydrocarbon bond activation reactions have developed rapidly. Because of their special structure and biological activity, the studies of nitrogen-containing and sulfur-containing heterocyclic compounds have become increasingly abundant.Therefore, more and more attention has been paid to the synthesis and modification of nitrogen-containing heterocyclic compounds by transition metal-catalyzed coupling reaction and hydrocarbon bond activation reaction.In this paper, the synthesis of pyrazolyl thiazide derivatives, isoquinoline derivatives, nitrogen-containing heterocyclic compounds and the modification of indoline derivatives were studied in detail.The results are as follows: a new method for the synthesis of pyrazolium thiazide derivatives by a "one pot two step method" with three components catalyzed by copper has been developed.In this reaction, a cheap and easily obtained 1-hali-2-halophenyl-3-alkylpropyl-2-acetyne-1-one derivative was used, hydrazine hydrochloride and 尾 -dithiomethyl ester as substrate materials, copper iodide as catalyst, cesium carbonate as base and acetonitrile as solvent, under mild conditions.The corresponding pyrazolium thiazide derivatives can be successfully synthesized from the three components in two steps and one pot.The target product contains functional functional groups such as carbonyl or halogen, which provides convenience and possibility for further modification.A new method for the synthesis of isoquinoline derivatives catalyzed by iridium is reported in this paper. The method can realize the series reaction of hydrocarbon bond activation and cyclization under the catalysis of iridium catalyst.Isoquinoline derivatives were synthesized by using easily obtained benzoimide derivatives and 偽 -diazo carbonyl compounds as raw materials, [Cp*IrCl2] 2 as catalyst, silver hexafluoroantimonate as additive and methanol as solvent under mild conditions.The reaction showed excellent tolerance for different functional groups and simple separation, which provided a new route for the synthesis of isoquinoline derivatives.A high efficient and practical rhodium-catalyzed amination of indoline C-7 was developed.In this reaction, the amination of indoline C-7 was realized under mild conditions by using benzo-iso-VA derivatives as amination reagent, indoline derivatives as reaction substrate, [Cp*RhCl2] 2 as catalyst, silver hexafluoroantimonate as additive, tetrahydrofuran as solvent, and mild conditions.The corresponding target products have functional functional groups such as amino, carbonyl, aldehyde, halogen or nitro, which can be modified more deeply or play an important role in the field of drug synthesis.A simple and practical method was developed, using aryl azole and 偽 -diazo carbonyl compounds as substrates, [Cp*RhCl2] 2 as catalyst, silver hexafluoroantimonate as additive, tetrahydrofuran as solvent, under mild conditions.The valuable nitrogen-containing dense heterocyclic compounds were synthesized by continuous C-H bond activation and cyclization catalyzed by RhCII.In this scheme, aryl azoles are used, including pyrazole, benzimidazole and 1-triazole, and most pyrazoles can react smoothly and effectively under mild conditions.This provides a new alternative method for the construction of a variety of potential bioactive heterocyclic compounds containing nitrogen for drug candidate screening.
【學(xué)位授予單位】：沈陽師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O626

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本文編號：1735008