發(fā)布時(shí)間：2018-01-08 07:39

  本文關(guān)鍵詞：烯烴氫羧化反應(yīng)研究　出處：《南京大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 氫羧化 氫酯化 區(qū)域選擇性 烯胺 烯烴

【摘要】：羰基化反應(yīng)作為一類重要的基元反應(yīng),已經(jīng)成為實(shí)驗(yàn)室基礎(chǔ)研究和工業(yè)生產(chǎn)中的焦點(diǎn)。其中,烯烴羰基化反應(yīng)以其原子經(jīng)濟(jì)性的特點(diǎn)而被廣泛研究,隨著對(duì)該領(lǐng)域的不斷深入研究,其作為一種功能廣泛且簡(jiǎn)便的有機(jī)合成方法,在復(fù)雜有機(jī)分子合成中的應(yīng)用更加廣泛。通常,羰基化反應(yīng)使用CO作為羰基源,然而,該方法的主要缺點(diǎn)是CO有毒且易燃,使其在儲(chǔ)存、運(yùn)輸以及操作上都存在困難,該缺點(diǎn)大大限制了羰基化反應(yīng)的實(shí)際應(yīng)用和發(fā)展。因此,發(fā)展一種安全、高效、易操作且不使用CO氣體的烯烴羰基化反應(yīng)已成為當(dāng)下的研究熱點(diǎn)。本論文主要是圍繞非CO的區(qū)域選擇性羰基化反應(yīng)展開的,主要工作包括以下三部分:1.研究了鈀催化的1,1-二取代烯胺的區(qū)域選擇性的氫羧化反應(yīng)。該反應(yīng)中以簡(jiǎn)單易得的HCOOPh來代替?zhèn)鹘y(tǒng)羰基化反應(yīng)中CO的使用,使得反應(yīng)操作簡(jiǎn)單安全。研究發(fā)現(xiàn),該反應(yīng)的反應(yīng)條件溫和,當(dāng)使用0.5 mol%APD為催化劑,2 mol%DPEphos為膦配體,在0.2 equiv HCOOPh和2 equiv HCOOH存在下,1,1-二取代烯胺可順利進(jìn)行氫羧化反應(yīng)。該反應(yīng)適用的底物類型廣泛,對(duì)各種鏈狀烷基取代、環(huán)狀烷基取代、芳基取代和萘基取代的烯胺都表現(xiàn)出很好的反應(yīng)活性,以60-98%收率得到相應(yīng)高區(qū)域選擇性的羧酸產(chǎn)物,且所得β-氨基酸通過肼解即可以98%的收率得到相應(yīng)的游離β-氨基酸。當(dāng)使用2.5 mol%APD為催化劑,10 mol%DPEphos為膦配體,1.2 equiv HCOOPh為羰基源時(shí),1,1-二取代烯胺可順利進(jìn)行氫酯化反應(yīng),高區(qū)域選擇性的得到相應(yīng)的β-氨基酯,產(chǎn)率高達(dá)86%。2.研究了鈀催化的1,2-二取代烯胺的區(qū)域選擇性的氫羧化反應(yīng)。β-氨基酸廣泛存在于自然界中,是具有生物活性及藥物活性分子的重要組成部分,因此,快速高效的合成β-氨基酸對(duì)于生物醫(yī)學(xué)和藥物化學(xué)都具有重要意義。本論文通過1,2-二取代烯胺的氫羧化反應(yīng)可以快速高效的合成各種β2-氨基酸。該反應(yīng)中不需使用到不易存儲(chǔ)、運(yùn)輸和操作的有毒易燃?xì)怏wCO。研究發(fā)現(xiàn),配體對(duì)反應(yīng)活性具有決定性的作用。1,2-二取代烯胺在APD(2.5mol%)和 PPh3(20mol%)的催化下,與 HCOOPh(1.2equiv)和 HCOOH(2.0 equiv)發(fā)生氫羧反應(yīng),能夠以68-99%的收率高區(qū)域選擇性的得到β2-氨基酸。此外,本論文還研究了烯烴的幾何構(gòu)型對(duì)氫竣化反應(yīng)的影響,發(fā)現(xiàn)不論是順式烯胺還是反式烯胺,進(jìn)行氫羧化反應(yīng)都具有較高的區(qū)域選擇性,且所得產(chǎn)物相同,同時(shí)順式-1,2-二取代烯胺表現(xiàn)出更高的反應(yīng)活性。同樣,所得氨基酸在水合肼作用下肼解能夠以98%的收率得到相應(yīng)的游離β2-氨基酸。3.研究了鈀催化的1,2-二芳基乙烯類化合物的氫羧化反應(yīng)。1,2-二芳基取代烯烴可以分為對(duì)稱和非對(duì)稱的,在對(duì)稱的1,2-二芳基取代烯烴的氫羧化反應(yīng)中,只需解決其反應(yīng)活性問題,而在非對(duì)稱的1,2-二芳基取代烯烴的氫羧化反應(yīng)中,除了需要解決反應(yīng)活性問題,還需解決區(qū)域選擇性的問題。本論文通過對(duì)過渡金屬、配體、溫度等方面的調(diào)控,已經(jīng)順利解決對(duì)稱的1,2-二芳基取代烯烴氫羧化反應(yīng)的活性問題,非對(duì)稱的1,2-二芳基取代烯烴氫羧化反應(yīng)還需進(jìn)一步研究。
[Abstract]:Carbonylation reaction as a kind of important elementary chemical reactions, has become the focus of the laboratory study and industrial production. Among them, olefin carbonylation reaction to its atom economy and has been studied, with the deepening of research in this field, as a function of the organic synthesis method widely and simple and the application in the synthesis of complex organic molecules in the more widely. Usually, the carbonylation reaction using CO as a carbonyl source, however, the main drawback of this method is CO toxic and flammable, so that in the storage, transportation and operation difficulties exist, practical application and development of the disadvantages greatly limits the carbonylation reaction. Therefore and the development of a safe, efficient, easy to operate and carbonylation of olefins without the use of CO gas has become a hot research topic at present. This thesis mainly focuses on the regioselective carbonylation reactions show non CO open, mainly The work includes the following three parts: 1. research on the hydrogen carboxylation reaction of palladium catalyzed regioselective 1,1- two substituted enamines. The reaction is easy to use the HCOOPh to replace the traditional carbonylation of CO, the reaction is simple and safe operation. The study found that mild reaction condition of the reaction, when using mol%APD 0.5 as catalyst, 2 mol%DPEphos phosphine ligands, in the presence of 0.2 equiv HCOOPh and 2 equiv HCOOH, two 1,1- substituted enamines can be carried out smoothly. The hydrogen carboxylation reaction reaction of suitable substrate types widely, instead of different kinds of chain alkyl, cyclic alkyl substituted enamines, aryl substituted naphthyl substituted and the exhibit good reaction activity, obtained the corresponding carboxylic acid product with high regioselectivity in 60-98% yield, and the yield obtained by hydrazinolysis of beta amino acids that can get 98% free beta corresponding amino acids. When using 2.5 mol% APD as catalyst Agent, 10 mol%DPEphos for 1.2 equiv HCOOPh phosphine ligands, carbonyl source, 1,1- two substituted enamines can be smoothly carried out hydrogen esterification reaction, high regioselectivity of corresponding beta amino ester, high yield of 86%.2. carboxylation reaction of hydrogen by palladium catalyzed regioselective 1,2- two substituted enamines beta. Amino acids are widespread in nature, is an important part of the activity, with molecular biological activity and drug so fast and efficient synthesis of beta amino acids for biomedical and pharmaceutical chemistry are of great significance. This paper through 1,2- two carboxylation reaction instead of hydrogen enamines can quickly and efficiently synthesize a variety of amino acids. The 2- beta in response to the need to use is not easy to store, transport and CO. of toxic flammable gas operation that has decisive role in.1,2- two ligand substituted enamines on reaction activity in APD (2.5mol%) and PPh3 (20mol%). Under the HCOOPh, and (1.2equiv) and HCOOH (2 equiv) hydrogen decarboxylation, with selective high yield regions of 68-99% are 2- beta amino acids. In addition, the effect of geometry on hydrogen olefin reaction method is studied in this paper, either cis or trans enamine enamine, regioselectivity has higher hydrogen carboxylation reaction, and the products of the same, and two cis -1,2- substituted enamines showed higher reactivity. Similarly, the amino acid can hydrazinolysis in hydrazine hydrate under the action of the 98% of the yield of the corresponding free beta amino acid.3. 2- on palladium hydrogen carboxylation the catalytic reaction of.1,2- two 1,2- two aryl aryl vinyl compounds substituted olefins can be divided into symmetric and asymmetric and symmetric 1,2- in two aryl substituted hydrogen carboxylation reaction of olefins, only need to solve the problem in the non reactive, and to call 1,2- two Aryl substituted hydrogen carboxylation reaction of olefins, in addition to the need to solve the problem of reactive, but also need to solve the problem. The regioselectivity of the ligands on the transition metal, the temperature control, and other aspects of the problem has been solved successfully, the activity of 1,2- two symmetry aryl substituted olefin hydrogen carboxylation reaction, carboxylation of olefins the reaction also need further study to replace the non symmetric 1,2- two aryl.

【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25

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