發(fā)布時(shí)間：2018-07-20 20:08

【摘要】：一鍋催化反應(yīng)由于其具有原子利用率高和操作步驟少的特點(diǎn)已經(jīng)吸引很多研究者的關(guān)注。然而,昂貴的有機(jī)金屬配合物和產(chǎn)品污染等固有的缺點(diǎn),阻礙了其在工業(yè)過(guò)程中應(yīng)用。因此,發(fā)展一個(gè)把金屬固載化的策略克服這些缺點(diǎn)是非常有必要的。介孔硅材料作為一種支持固定有機(jī)金屬配合物在催化中顯示了一些良好的功能,而其中蛋殼結(jié)構(gòu)的納米材料,它具有可移動(dòng)的功能化的核和外層包覆著功能化的殼,賦予了它在納米材料上的獨(dú)特特性,使得蛋殼結(jié)構(gòu)納米材料在催化領(lǐng)域得到了廣泛應(yīng)用。本論文主要分為以下兩部分:(1)雙功能負(fù)載型金屬催化劑的制備及其在Sonogashira偶聯(lián)-不對(duì)稱氫轉(zhuǎn)移串聯(lián)反應(yīng)的應(yīng)用:我們利用蛋殼結(jié)構(gòu)材料而設(shè)計(jì)了一種雙功能的異相催化劑,克服了鈀釕雙金屬化合物的不兼容性,從而實(shí)現(xiàn)了鈀催化Sonogashira偶聯(lián)及釕催化的一鍋不對(duì)稱氫轉(zhuǎn)移反應(yīng)。因?yàn)榈皻そY(jié)構(gòu)的獨(dú)特性質(zhì),雙功能催化劑可以將金屬鈀和釕分別負(fù)載于蛋殼材料的殼與核上,從而可以在偶聯(lián)及其一鍋不對(duì)稱催化構(gòu)建炔醇起到協(xié)調(diào)作用,且目標(biāo)產(chǎn)物ee值可高達(dá)99%。此外催化劑可以回收利用,而且至少循環(huán)使用八次而催化劑的催化活性沒(méi)有明顯下降。(2)雙功能負(fù)載型金屬催化劑的制備及其在Suzuki-Miyaura偶聯(lián)-不對(duì)稱氫轉(zhuǎn)移串聯(lián)反應(yīng)的應(yīng)用:我們通過(guò)一種簡(jiǎn)單的方法成功合成了一種負(fù)載納米鈀粒子及手性釕金屬的雙功能催化劑,并將催化劑應(yīng)用于Suzuki偶聯(lián)及其不對(duì)稱串聯(lián)反應(yīng)中,實(shí)現(xiàn)了一鍋一步合成手性聯(lián)芳醇,且目標(biāo)產(chǎn)物ee值可高達(dá)97%,此外催化劑循環(huán)使用多次后而催化劑的催化活性沒(méi)有明顯下降。
[Abstract]:One-pot catalytic reaction has attracted the attention of many researchers due to its high atomic utilization and low operational steps. However, its application in industrial processes is hampered by the inherent disadvantages of expensive organometallic complexes and product pollution. Therefore, it is necessary to develop a strategy of metal immobilization to overcome these shortcomings. Mesoporous silicon, as a support for the immobilization of organometallic complexes, has shown some good functions in the catalysis. Among them, the eggshell nanomaterials have movable functionalized nuclei and outer layers coated with functionalized shells. Because of its unique properties in nano-materials, eggshell nanomaterials have been widely used in the field of catalysis. This thesis is divided into the following two parts: (1) preparation of bifunctional supported metal catalyst and its application in Sonogashira coupling-asymmetric hydrogen transfer series reaction: we designed a bifunctional heterogeneous catalyst using eggshell structure. The incompatibility of palladium and ruthenium bimetallic compounds was overcome, and palladium catalyzed Sonogashira coupling and ruthenium catalyzed one-pot asymmetric hydrogen transfer reaction were realized. Because of the unique properties of the eggshell structure, the bifunctional catalyst can load palladium and ruthenium onto the shell and nucleus of the eggshell material respectively, which can coordinate the formation of acetylene alcohol in the coupling and its one-pot asymmetric catalysis. The ee value of the target product can be as high as 99%. In addition, the catalyst can be recycled, Moreover, the catalytic activity of the catalyst did not decrease significantly without at least eight cycles of recycling. (2) preparation of the bifunctional supported metal catalyst and its application in Suzuki-Miyaura coupling-asymmetric hydrogen transfer series reaction: we adopted a simple Methods A bifunctional catalyst supported on nanometer palladium particles and chiral ruthenium metal was successfully synthesized. The catalyst was used in Suzuki coupling and its asymmetric series reaction to realize the one-pot one-step synthesis of chiral biaryl alcohol, and the ee value of the target product could be as high as 97%. In addition, the catalytic activity of the catalyst did not decrease obviously after repeated cyclic use of the catalyst.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O621.251

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 王亮;魯珍;;手性二級(jí)胺催化的不對(duì)稱串聯(lián)反應(yīng)研究進(jìn)展[J];江漢大學(xué)學(xué)報(bào)(自然科學(xué)版);2013年05期

2 高蒙;楊雁;王紫華;張冬雪;吳柳明;鄧聰;舒文明;吳安心;;基于異源自分類串聯(lián)反應(yīng)集成策略構(gòu)筑不對(duì)稱的1,4-二氫吡啶衍生物[J];高等學(xué)�；瘜W(xué)學(xué)報(bào);2011年09期

3 胡生泳;串聯(lián)反應(yīng)產(chǎn)物分布優(yōu)化研究[J];廣東化工;2005年10期

4 章瑛;王宏亮;吳建一;;基于串聯(lián)反應(yīng)的吡蟲(chóng)啉新合成工藝研究[J];化學(xué)通報(bào);2014年09期

5 ;Cu-催化的不對(duì)稱串聯(lián)反應(yīng)研究取得重要進(jìn)展[J];中國(guó)材料進(jìn)展;2010年06期

6 王早;劉晨江;王吉德;王娜;;牛血清蛋白催化Michael-Aldol串聯(lián)反應(yīng)的研究[J];化學(xué)研究與應(yīng)用;2012年07期

7 韓瑩;孫晶;孫巖;高紅;顏朝國(guó);;β-烯胺酯為關(guān)鍵中間體的串聯(lián)反應(yīng)研究進(jìn)展[J];有機(jī)化學(xué);2012年09期

8 萬(wàn)致富;;手性叔胺催化不對(duì)稱串聯(lián)反應(yīng)構(gòu)建氧化吲哚螺環(huán)化合物的研究進(jìn)展[J];遼寧化工;2014年08期

9 郭金波;張淅蕓;陳慶華;;基于5-孟氧基-3-溴-2(5H)-呋喃酮的環(huán)丙烷合成方法研究:碳親核試劑啟動(dòng)的不對(duì)稱串聯(lián)反應(yīng)[J];化學(xué)學(xué)報(bào);2006年19期

10 王建武,賈炯,候殿杰,李紅梅,尹軍;一個(gè)新的制備咪唑并[1,5-a]吡啶衍生物的串聯(lián)反應(yīng)[J];有機(jī)化學(xué);2003年02期

相關(guān)會(huì)議論文 前10條

1 壽王鴿;楊允蕓;王彥廣;;醛與芳胺的串聯(lián)反應(yīng)合成菲啶和喹啉[A];中國(guó)化學(xué)會(huì)第二十五屆學(xué)術(shù)年會(huì)論文摘要集（上冊(cè)）[C];2006年

2 林旭鋒;崔孫良;王彥廣;;苯胺與環(huán)烯醚的串聯(lián)反應(yīng)合成1,2,3,4-四氫喹啉[A];中國(guó)化學(xué)會(huì)第二十五屆學(xué)術(shù)年會(huì)論文摘要集（上冊(cè)）[C];2006年

3 聶凜凜;房輝輝;劉欽;戴小鴦;吳小余;;串聯(lián)反應(yīng)在構(gòu)建吲哚雜環(huán)中的應(yīng)用[A];中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第6分會(huì)場(chǎng)摘要集[C];2012年

4 吳R，

本文編號(hào)：2134630