过渡金属催化的碳—磷键构筑反应研究
发布时间：2018-12-13 04:12
【摘要】：有机膦化合物因其独特的化学性质和生物活性而被广泛应用于有机合成化学和生命科学中。因此,发展简单高效的策略来构筑碳-磷键一直倍受研究关注。而通过过渡金属催化碳-氢键直接官能团化反应构筑碳-磷键是最具原子经济性和环境友好性的策略。本论文概述了近年来过渡金属催化碳-磷键构筑反应的研究进展和详细介绍了过渡金属催化四种不同方法构筑碳-磷键的研究。本论文包括以下五部分:一、分类总结了过渡金属催化碳-磷键构筑反应的研究进展。内容主要根据不同的反应类型对近些年发展的过渡金属催化碳-磷键构筑反应进行了概述。二、系统研究了铑/镍催化烯丙胺异构化氢磷酰化构筑碳-磷键的反应。该反应通过烯丙胺异构化成烯胺的历程一步构建碳-磷键来合成α-氨基磷酸酯。初步的机理研究后,我们提出了反应可能经历一个π-烯丙基类型机理。三、系统研究了银催化炔丙醇磷酰化合成磷酰化联烯的反应。该反应通过Meyer Schuster重排合成了一系列的磷酰化联烯类化合物。并且反应不需要碱和配体的参与,水是唯一副产物。四、系统研究了铜催化烯烃C-H键氧化磷酰化反应。该反应以惰性的烯烃为底物,通过催化剂和氧化剂的调控高效专一地合成烯基磷氧化合物,初步机理探究表明反应可能经历一个自由基的历程。五、系统研究了银催化磷自由基对1,6-二烯串联环化的反应。该反应可以高区域选择性和立体选择性合成含磷的五元环化合物,初步机理探究表明反应可能经历一个自由基的历程。
[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 伪 -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.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O627.51
，
本文编号：2375854
[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 伪 -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.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O627.51
，
本文编号：2375854
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