双功能三唑卡宾前驱体的合成及其在不对称硅基化中的应用研究
发布时间：2018-08-07 09:18
【摘要】：在有机化学反应研究中,催化形成新的化学键是非常重要的。催化剂可以使反应进行的更加容易,选择性更好而且环境友好,使用高效的催化剂可以发展许多新的合成策略。同时,将催化剂应用于经典反应得到的结果往往让人惊喜。而不对称催化更是催化研究的重中之重。卡宾类催化剂是有机化学领域中研究最多的催化剂之一。从第一个卡宾催化剂合成以来,卡宾被广泛应用于不对称催化反应中。与膦配体和氮磷配体相比卡宾具有独特的电子效应,可以应用于有机金属催化和有机催化反应中。目前广泛应用的氮杂环卡宾催化剂是三氮唑卡宾。手性催化剂的特征是都包含至少一个手性元素,我们将带有中心手性的卡宾引入[2.2]环仿中,得到了一类新型双手性配体。该配体可以与铜形成配合物催化反应,也可以单独进行有机催化,是一类新型的两用催化剂。我们课题组利用该类配体催化不饱和羰基化合物的硼化反应和硅基化反应都得到了很好的结果。水是地球上最丰富的分子之一。它非常便宜,特别是与有机溶剂相比,水是不可燃和无毒的,而且具有大的热容量,所以如果适当使用水作为有机反应溶剂可带来许多环境益处和意想不到的结果。而我们以前合成的配体在水相中均不能进行催化反应。因此我们想尝试对以前合成的三氮唑盐进行修饰,得到一种双功能的新型三氮唑盐,希望能将其应用于水相不对称硅基化的反应中。本论文包括以下几部分内容。1.对卡宾催化及卡宾在水相中的催化进行归纳综述自从稳定的卡宾被Bertrand等人首次报道以来,N-杂环卡宾(NHCs)在有机催化中的得到了非常广泛的应用。卡宾配体可以与过渡金属结合催化许多反应,也可以进行有机催化反应,其催化的反应也从安息香缩合反应等零星反应到广泛使用。有机反应在水或水性介质中进行可以带来许多益处,例如产物在水中的溶解度较低,更容易分离产物;水是更安全的反应介质,可以降低成本等。2.双功能三氮唑盐的合成以拆分好的SP-4-氨基-12-溴[2.2]环仿为原料,通过重氮化反应得到重氮盐,再与LiBr反应得到Sp-4,12-二溴[2.2]环仿。Sp-4,12-二溴[2.2]环仿与二苯酮腙反应得到Sp-4-二苯酮腙-12-溴[2.2]环仿,然后通过加甲酰化反应得到Sp-4-(N-甲酰基二苯酮腙基)-12-溴[2.2]环仿。上步产物与2-羟基苯硼酸反应后,酸解得到SP-4-(N-甲酰肼基)-12-(2-苯酚基)[2,2]环仿盐酸盐,然后与S-叔丁基吗啉酮亚胺醚反应得到三唑盐(S,Sp)-2。(S,Sp)-3的合成与上述步骤相同。3.双功能三氮唑卡宾催化芳香醛的不对称硅基化反应以DBU做碱,在水作溶剂的情况下,(S,Sp)-3可以催化芳香醛与硅试剂发生加成反应。并在最有条件下对底物进行了拓展,发现大多数的醛都可以得到高的收率和中等的er值。创新点1.我们合成了一系列新颖的基于[2.2]环仿的双功能三氮唑卡宾前驱体,并在环仿上成功引入活性基团。2.首次实现了水相中卡宾催化芳香醛的不对称硅基化反应,并取得了不错的收率和er值。
[Abstract]:In the study of organic chemical reactions, it is very important to catalyze the formation of new chemical bonds. The catalyst can make the reaction easier, more selective and environmentally friendly, and many new synthetic strategies can be developed using high efficient catalysts. At the same time, the results of the application of the catalyst to the classical reaction are often surprising. Symmetric catalysis is more important in catalytic research. CABBEEN catalyst is one of the most widely studied catalysts in the field of organic chemistry. Since the synthesis of the first CABBEEN catalyst, CABBEEN has been widely used in asymmetric catalytic reactions. Compared with phosphine ligands and nitrogen and phosphorus ligands, CABBEEN has a unique electronic effect and can be applied to organic gold. In the catalytic and organic catalytic reactions, the widely used nitrogen heterocyclic CABBEEN catalyst is three azoles CABBEEN. The chiral catalyst is characterized by at least one chiral element. We introduce a central chiral CABBEEN into the [2.2] cycle to obtain a new type of both hands. This ligand can catalyze the reaction of the ligand with copper. It is a new type of dual use catalyst. Our group uses this kind of ligand to catalyze the boronizing reaction and silicylation of unsaturated carbonyl compounds. Water is one of the richest molecules on earth. It is very cheap, especially when compared with organic solvents, water is not flammable. It is nontoxic and has large thermal capacity, so if proper use of water as an organic reaction solvent can bring many environmental benefits and unexpected results. And our previously synthesized ligands are not catalyzed in the aqueous phase. Therefore, we would like to try to modify the previously synthesized three azoles to get a double function. The new three azoles of three azoles are expected to be applied to the reaction of asymmetric silylation in aqueous phase. This paper includes the following parts of the summary of the following contents:.1. catalysis and the catalysis of CABBEEN in the water phase. Since the stable CABBEEN was first reported by Bertrand et al., the N- heterocyclic CABBEEN (NHCs) has been obtained in the organic catalysis A wide range of applications. CABBEEN ligands can catalyze many reactions with transition metals, as well as organic catalysis, and their catalytic reactions are also widely used from the benzoin condensation reaction to a wide range of use. Organic reactions can bring many benefits in water or aqueous media, such as low solubility in water and more capacitive products. The water is a more safe product; water is a more safe reaction medium, it can reduce the cost of.2. bifunctional three azoles, such as the synthesis of a good SP-4- amino -12- bromine [2.2] ring as raw material, the diazonium salt is obtained by the diazotization reaction, and the reaction of Sp-4,12- dibromine [2.2] ring like.Sp-4,12- dibrominated [2.2] ring and two benzophenone hydrazone reacts with LiBr to obtain Sp-4-. The two benzophenone hydrazone -12- bromine [2.2] ring is imitated, and then the Sp-4- (N- formyl two benzophenone hydrazone) -12- bromine [2.2] ring is obtained by the formylation reaction. After the reaction of the step product and 2- hydroxybenzboric acid, SP-4- (N- formyl hydrazine) -12- (2- phenol) [2,2] ring imitating hydrochloride is obtained, and then three azolium salts are reacted with tertiary butyl morpholone imide ether. (S, Sp) -3 synthesis and the same.3. double function three nitroazole CABBEEN catalyzes the asymmetric silicylation of aromatic aldehydes with DBU. In the case of water as solvent, (S, Sp) -3 can catalyze the addition reaction of aromatic aldehydes with silicon reagents. And the substrate is expanded under the most conditions, and most aldehydes can be obtained high. The yield and medium Er value. Innovation 1. we synthesized a series of novel double functional three azazole CABBEEN precursors based on [2.2], and successfully introduced the active group.2. in the cyclic imitation for the first time to realize the asymmetric silicylation of aromatic aldehyde catalyzed by CABBEEN in the water phase, and obtained a good yield and ER value.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
[Abstract]:In the study of organic chemical reactions, it is very important to catalyze the formation of new chemical bonds. The catalyst can make the reaction easier, more selective and environmentally friendly, and many new synthetic strategies can be developed using high efficient catalysts. At the same time, the results of the application of the catalyst to the classical reaction are often surprising. Symmetric catalysis is more important in catalytic research. CABBEEN catalyst is one of the most widely studied catalysts in the field of organic chemistry. Since the synthesis of the first CABBEEN catalyst, CABBEEN has been widely used in asymmetric catalytic reactions. Compared with phosphine ligands and nitrogen and phosphorus ligands, CABBEEN has a unique electronic effect and can be applied to organic gold. In the catalytic and organic catalytic reactions, the widely used nitrogen heterocyclic CABBEEN catalyst is three azoles CABBEEN. The chiral catalyst is characterized by at least one chiral element. We introduce a central chiral CABBEEN into the [2.2] cycle to obtain a new type of both hands. This ligand can catalyze the reaction of the ligand with copper. It is a new type of dual use catalyst. Our group uses this kind of ligand to catalyze the boronizing reaction and silicylation of unsaturated carbonyl compounds. Water is one of the richest molecules on earth. It is very cheap, especially when compared with organic solvents, water is not flammable. It is nontoxic and has large thermal capacity, so if proper use of water as an organic reaction solvent can bring many environmental benefits and unexpected results. And our previously synthesized ligands are not catalyzed in the aqueous phase. Therefore, we would like to try to modify the previously synthesized three azoles to get a double function. The new three azoles of three azoles are expected to be applied to the reaction of asymmetric silylation in aqueous phase. This paper includes the following parts of the summary of the following contents:.1. catalysis and the catalysis of CABBEEN in the water phase. Since the stable CABBEEN was first reported by Bertrand et al., the N- heterocyclic CABBEEN (NHCs) has been obtained in the organic catalysis A wide range of applications. CABBEEN ligands can catalyze many reactions with transition metals, as well as organic catalysis, and their catalytic reactions are also widely used from the benzoin condensation reaction to a wide range of use. Organic reactions can bring many benefits in water or aqueous media, such as low solubility in water and more capacitive products. The water is a more safe product; water is a more safe reaction medium, it can reduce the cost of.2. bifunctional three azoles, such as the synthesis of a good SP-4- amino -12- bromine [2.2] ring as raw material, the diazonium salt is obtained by the diazotization reaction, and the reaction of Sp-4,12- dibromine [2.2] ring like.Sp-4,12- dibrominated [2.2] ring and two benzophenone hydrazone reacts with LiBr to obtain Sp-4-. The two benzophenone hydrazone -12- bromine [2.2] ring is imitated, and then the Sp-4- (N- formyl two benzophenone hydrazone) -12- bromine [2.2] ring is obtained by the formylation reaction. After the reaction of the step product and 2- hydroxybenzboric acid, SP-4- (N- formyl hydrazine) -12- (2- phenol) [2,2] ring imitating hydrochloride is obtained, and then three azolium salts are reacted with tertiary butyl morpholone imide ether. (S, Sp) -3 synthesis and the same.3. double function three nitroazole CABBEEN catalyzes the asymmetric silicylation of aromatic aldehydes with DBU. In the case of water as solvent, (S, Sp) -3 can catalyze the addition reaction of aromatic aldehydes with silicon reagents. And the substrate is expanded under the most conditions, and most aldehydes can be obtained high. The yield and medium Er value. Innovation 1. we synthesized a series of novel double functional three azazole CABBEEN precursors based on [2.2], and successfully introduced the active group.2. in the cyclic imitation for the first time to realize the asymmetric silicylation of aromatic aldehyde catalyzed by CABBEEN in the water phase, and obtained a good yield and ER value.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
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