过渡金属催化碳—碳，碳—杂偶联反应研究
发布时间：2018-08-05 16:12
【摘要】：过渡金属催化C-C或C-X键的偶联反应为近年来有机化学家研究的热点。通过过渡金属催化有机小分子的转化,使其转变为具有特定功效的功能分子,对理论和应用研究都有非常重要的意义。本文综述了过渡金属催化的C-S键的活化反应、酮α-C-H活化反应、α,β-不饱和酸的脱羧反应,在此基础上开展了如下研究:1、钯催化的脱硫Sonogshira偶联反应在Pd(OAc)_2催化、CuI作为脱硫剂条件下,实现了巯基-N-杂环底物与端炔的脱硫Sonogshira偶联反应。各种取代的芳基、烷基炔和巯基-N-杂环底物都可以适用于该反应。该反应为Csp2-Csp键的构筑提供了有效的方法。机理研究表明,Pd插入到C-S键之间为该反应的决速步。2、铜催化的α-C-H酰氧基化反应发展了一种铜催化酮类化合物与端炔的α-C-H酰氧基化反应。反应以Cu(acac)_2位催化剂,TBHP为氧化剂,端炔作为酰氧基化试剂,以中等收率合成了一系列的酰氧基酮类化合物。基于机理研究实验,提出并理论研究了该反应的自由基机理。3、KI/K_2S_2O_8催化的α-C-H硫醚化反应在无过渡金属催化剂的条件下,室温实现了酮类化合物与硫醇的α-C-H硫醚化反应。该反应选择性高,条件温和,底物适用范围广,各种芳香或非芳香酮与芳香或杂环硫醇都适用于该反应。通过机理研究实验,提出了该反应的可能反应机理。4、铁催化的脱羧硝基化反应发展了一种Fe(Ⅲ)/pyridine催化的α,β-不饱和酸的脱羧硝基化反应。该方法反应收率高,底物适用范围广,为合成E-硝基烯类化合物提供了有效的方法。通过机理研究实验,证明了该反应的机理为自由基反应,并通过DFT研究对机理进行了理论研究。
[Abstract]:The coupling reaction of C-C or C-X bonds catalyzed by transition metals has been a hot spot of organic chemists in recent years. The transition metal catalyzes the transformation of small organic molecules into functional molecules with specific functions, which is of great significance for both theoretical and practical research. In this paper, the activation of C-S bond catalyzed by transition metals, the activation of ketone 伪 -C-H and the decarboxylation of 伪, 尾 -unsaturated acids have been reviewed. The following studies have been carried out on the following basis: the Sonogshira coupling reaction of desulphurization catalyzed by Pd (OAc) _ 1 and palladium was carried out under the condition of Pd (OAc) _ 2 as desulfurizer. The Sonogshira coupling reaction of thiol-N-heterocyclic substrates with terminal alkynes was realized. Various substituted aryl, alkyne and mercapto-N-heterocyclic substrates can be applied to this reaction. This reaction provides an effective method for the construction of Csp2-Csp bond. The mechanism study shows that the insertion of Pd into C-S bond is the fast step of the reaction. The copper-catalyzed 伪 -C-H acyloxylylation reaction develops a copper-catalyzed 伪 -C-H acylolylation reaction between ketones and alkynes. A series of acyloxyl ketones were synthesized in medium yield using Cu (acac) tip as oxidant and terminal acetylene as acyloxylation reagent. Based on the experimental results of mechanism study, the free radical mechanism of the reaction was proposed and theoretically studied. The reaction of 伪 -C-H sulfidation of ketones with mercaptan was realized at room temperature under the condition of no transition metal catalyst, and the reaction of 伪 -C-H sulfide catalyzed by Ki / K _ 2S _ 2S _ 2O _ 8 was carried out at room temperature. The reaction has high selectivity, mild conditions and a wide range of substrates. All kinds of aromatic or non-aromatic ketones and aromatic or heterocyclic mercaptans are suitable for the reaction. The possible reaction mechanism of the reaction was put forward. The iron catalyzed decarboxylation nitration developed a Fe (鈪，
本文编号：2166309
[Abstract]:The coupling reaction of C-C or C-X bonds catalyzed by transition metals has been a hot spot of organic chemists in recent years. The transition metal catalyzes the transformation of small organic molecules into functional molecules with specific functions, which is of great significance for both theoretical and practical research. In this paper, the activation of C-S bond catalyzed by transition metals, the activation of ketone 伪 -C-H and the decarboxylation of 伪, 尾 -unsaturated acids have been reviewed. The following studies have been carried out on the following basis: the Sonogshira coupling reaction of desulphurization catalyzed by Pd (OAc) _ 1 and palladium was carried out under the condition of Pd (OAc) _ 2 as desulfurizer. The Sonogshira coupling reaction of thiol-N-heterocyclic substrates with terminal alkynes was realized. Various substituted aryl, alkyne and mercapto-N-heterocyclic substrates can be applied to this reaction. This reaction provides an effective method for the construction of Csp2-Csp bond. The mechanism study shows that the insertion of Pd into C-S bond is the fast step of the reaction. The copper-catalyzed 伪 -C-H acyloxylylation reaction develops a copper-catalyzed 伪 -C-H acylolylation reaction between ketones and alkynes. A series of acyloxyl ketones were synthesized in medium yield using Cu (acac) tip as oxidant and terminal acetylene as acyloxylation reagent. Based on the experimental results of mechanism study, the free radical mechanism of the reaction was proposed and theoretically studied. The reaction of 伪 -C-H sulfidation of ketones with mercaptan was realized at room temperature under the condition of no transition metal catalyst, and the reaction of 伪 -C-H sulfide catalyzed by Ki / K _ 2S _ 2S _ 2O _ 8 was carried out at room temperature. The reaction has high selectivity, mild conditions and a wide range of substrates. All kinds of aromatic or non-aromatic ketones and aromatic or heterocyclic mercaptans are suitable for the reaction. The possible reaction mechanism of the reaction was put forward. The iron catalyzed decarboxylation nitration developed a Fe (鈪，
本文编号：2166309
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