過渡金屬催化碳—碳，碳—雜偶聯(lián)反應研究
發(fā)布時間：2018-08-05 16:12
【摘要】：過渡金屬催化C-C或C-X鍵的偶聯(lián)反應為近年來有機化學家研究的熱點。通過過渡金屬催化有機小分子的轉化,使其轉變?yōu)榫哂刑囟üπУ墓δ芊肿?對理論和應用研究都有非常重要的意義。本文綜述了過渡金屬催化的C-S鍵的活化反應、酮α-C-H活化反應、α,β-不飽和酸的脫羧反應,在此基礎上開展了如下研究:1、鈀催化的脫硫Sonogshira偶聯(lián)反應在Pd(OAc)_2催化、CuI作為脫硫劑條件下,實現(xiàn)了巰基-N-雜環(huán)底物與端炔的脫硫Sonogshira偶聯(lián)反應。各種取代的芳基、烷基炔和巰基-N-雜環(huán)底物都可以適用于該反應。該反應為Csp2-Csp鍵的構筑提供了有效的方法。機理研究表明,Pd插入到C-S鍵之間為該反應的決速步。2、銅催化的α-C-H酰氧基化反應發(fā)展了一種銅催化酮類化合物與端炔的α-C-H酰氧基化反應。反應以Cu(acac)_2位催化劑,TBHP為氧化劑,端炔作為酰氧基化試劑,以中等收率合成了一系列的酰氧基酮類化合物�；跈C理研究實驗,提出并理論研究了該反應的自由基機理。3、KI/K_2S_2O_8催化的α-C-H硫醚化反應在無過渡金屬催化劑的條件下,室溫實現(xiàn)了酮類化合物與硫醇的α-C-H硫醚化反應。該反應選擇性高,條件溫和,底物適用范圍廣,各種芳香或非芳香酮與芳香或雜環(huán)硫醇都適用于該反應。通過機理研究實驗,提出了該反應的可能反應機理。4、鐵催化的脫羧硝基化反應發(fā)展了一種Fe(Ⅲ)/pyridine催化的α,β-不飽和酸的脫羧硝基化反應。該方法反應收率高,底物適用范圍廣,為合成E-硝基烯類化合物提供了有效的方法。通過機理研究實驗,證明了該反應的機理為自由基反應,并通過DFT研究對機理進行了理論研究。
[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 偽 -C-H and the decarboxylation of 偽, 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 偽 -C-H acyloxylylation reaction develops a copper-catalyzed 偽 -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 偽 -C-H sulfidation of ketones with mercaptan was realized at room temperature under the condition of no transition metal catalyst, and the reaction of 偽 -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，
本文編號：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 偽 -C-H and the decarboxylation of 偽, 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 偽 -C-H acyloxylylation reaction develops a copper-catalyzed 偽 -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 偽 -C-H sulfidation of ketones with mercaptan was realized at room temperature under the condition of no transition metal catalyst, and the reaction of 偽 -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，
本文編號：2166309
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