【摘要】：有機(jī)膦化合物因其獨(dú)特的化學(xué)性質(zhì)和生物活性而被廣泛應(yīng)用于有機(jī)合成化學(xué)和生命科學(xué)中。因此,發(fā)展簡(jiǎn)單高效的策略來(lái)構(gòu)筑碳-磷鍵一直倍受研究關(guān)注。而通過(guò)過(guò)渡金屬催化碳-氫鍵直接官能團(tuán)化反應(yīng)構(gòu)筑碳-磷鍵是最具原子經(jīng)濟(jì)性和環(huán)境友好性的策略。本論文概述了近年來(lái)過(guò)渡金屬催化碳-磷鍵構(gòu)筑反應(yīng)的研究進(jìn)展和詳細(xì)介紹了過(guò)渡金屬催化四種不同方法構(gòu)筑碳-磷鍵的研究。本論文包括以下五部分:一、分類總結(jié)了過(guò)渡金屬催化碳-磷鍵構(gòu)筑反應(yīng)的研究進(jìn)展。內(nèi)容主要根據(jù)不同的反應(yīng)類型對(duì)近些年發(fā)展的過(guò)渡金屬催化碳-磷鍵構(gòu)筑反應(yīng)進(jìn)行了概述。二、系統(tǒng)研究了銠/鎳催化烯丙胺異構(gòu)化氫磷酰化構(gòu)筑碳-磷鍵的反應(yīng)。該反應(yīng)通過(guò)烯丙胺異構(gòu)化成烯胺的歷程一步構(gòu)建碳-磷鍵來(lái)合成α-氨基磷酸酯。初步的機(jī)理研究后,我們提出了反應(yīng)可能經(jīng)歷一個(gè)π-烯丙基類型機(jī)理。三、系統(tǒng)研究了銀催化炔丙醇磷�；铣闪柞；�(lián)烯的反應(yīng)。該反應(yīng)通過(guò)Meyer Schuster重排合成了一系列的磷�；�(lián)烯類化合物。并且反應(yīng)不需要堿和配體的參與,水是唯一副產(chǎn)物。四、系統(tǒng)研究了銅催化烯烴C-H鍵氧化磷�；磻�(yīng)。該反應(yīng)以惰性的烯烴為底物,通過(guò)催化劑和氧化劑的調(diào)控高效專一地合成烯基磷氧化合物,初步機(jī)理探究表明反應(yīng)可能經(jīng)歷一個(gè)自由基的歷程。五、系統(tǒng)研究了銀催化磷自由基對(duì)1,6-二烯串聯(lián)環(huán)化的反應(yīng)。該反應(yīng)可以高區(qū)域選擇性和立體選擇性合成含磷的五元環(huán)化合物,初步機(jī)理探究表明反應(yīng)可能經(jīng)歷一個(gè)自由基的歷程。
[Abstract]:Organic phosphine compounds are widely used in organic synthesis chemistry and life sciences because of their unique chemical properties and biological activities. Therefore, the development of simple and efficient strategies for the construction of carbon-phosphorus bonds has attracted much attention. It is the most economical and environment-friendly strategy to construct carbon-phosphorus bond by direct functionalization of carbon-hydrogen bond catalyzed by transition metal. In this paper, the recent progress of transition metal-catalyzed carbon-phosphorus bond construction is reviewed, and four different methods of transition metal-catalyzed carbon-phosphorus bond construction are introduced in detail. This thesis includes five parts as follows: 1. The progress of transition metal catalyzed C-P bond construction is summarized. The recent development of transition metal catalyzed C-P bond construction was summarized according to different reaction types. Secondly, rhodium / nickel catalyzed isomerization of allylamine to hydrophosphorylation to form carbon-phosphorus bond was systematically studied. Through the isomerization of allylamine to enamine, a carbon-phosphorus bond was constructed to synthesize 偽 -aminophosphate ester. After a preliminary study of the mechanism, we suggest that the reaction may undergo a 蟺-allyl type mechanism. Third, silver catalyzed phosphorylation of propargyl alcohol to phosphodiene was systematically studied. A series of phosphoryldiene compounds were synthesized by Meyer Schuster rearrangement. Moreover, the reaction does not require the participation of alkali and ligand, water is the only by-product. Fourthly, the phosphorylation of C-H bond of olefins catalyzed by copper was systematically studied. Using inert olefin as substrate, alkenyl phosphates were synthesized specifically and efficiently through the regulation of catalyst and oxidant. The preliminary mechanism of the reaction indicated that the reaction may undergo a free radical process. Fifthly, the silver catalyzed reaction of phosphorus radical to the series cyclization of 1 ~ (6) -diene was studied systematically. This reaction can be used to synthesize pentacyclic compounds containing phosphorus with high regioselectivity and stereoselectivity. The preliminary mechanism of the reaction indicates that the reaction may undergo a free radical process.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O627.51
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本文編號(hào)：2375854