BINAP嵌入的多孔有机聚合物在多相不对称氢化反应中的作用（英文）
发布时间：2019-03-16 18:35
【摘要】：手性多孔有机聚合物具有较高的稳定性和催化活性,广泛用于多相不对称催化中.目前研究多集中在合成具有微孔结构的聚合物,而少有具有多种孔道结构(包含介孔和微孔)的聚合物的报道.之前我们报道了乙烯基修饰的BINAP配体,(S)-5,5’-divinyl-BINAP,将其与不同单体共聚后得到了一系列具有不同孔结构的有机聚合物.其负载的Rh基催化剂在苯乙烯不对称氢甲酰化反应中,表现出比均相更高的产物对映体选择性.本文采用不同的溴代步骤,合成了(S)-4,4’-divinyl-BINAP配体.将这两种具有乙烯基官能团的手性配体按相同的摩尔比与二乙烯基苯(DVB)共聚,得到两种不同的有机聚合物.负载[RuCl_2(benzene)]_2后,分别得到Ru/4-BINAP@POPs和Ru/5-BINAP@POPs-1.采用一锅法合成了催化剂Ru/5-BINAP@POPs-2;以[RuCl_2(p-cyme)]_2和RuCl_3分别合成了Ru/5-BINAP@POPs-3和Ru/5-BINAP@POPs-4催化剂.N2物理吸附结果显示,Ru/4-BINAP@POPs和Ru/5-BINAP@POPs-1催化剂具有相似的孔道结构;而采用一锅法合成的Ru/5-BINAP@POPs-2催化剂的介孔孔径较大.4-BINAP@POPs和5-BINAP@POPs聚合物的~(13)C核磁显示,其均在145,137和128 ppm处有明显的吸收峰,可归结为萘环和苯环上的碳振动峰;在44.0 ppm处的峰归属为亚甲基上的碳振动峰;31P核磁显示,在聚合物中P基本没有被氧化.将所得到的Ru/POPs催化剂应用于乙酰乙酸甲酯的多相不对称加氢反应中,Ru/5-BINAP@POPs-1催化剂具有与Ru/4-BINAP@POPs更快的反应速率.在相同反应条件下,催化剂活性大小为Ru/5-BINAP@POPs-1Ru/5-BINAP@POPs-3Ru/5-BINAP@POPs-4Ru/5-BINAP@POPs-2.另外Ru/5-BINAP@POPs-1催化剂对β-酮酸酯有着较好的底物适应性,且在釜式反应中可循环使用6次而活性基本不变.分析发现,使用前后的催化剂均没有明显的Ru Ru键的存在.表明Ru金属高度分散于催化剂上,且具有较高的稳定性,金属不易聚集,这也是其具有高活性和稳定性的原因.
[Abstract]:Chiral porous organic polymers have high stability and catalytic activity and are widely used in heterogeneous asymmetric catalysis. At present, most of the studies are focused on the synthesis of polymers with microporous structure, but few reports of polymers with multiple pore structures (including mesoporous and microporous) have been reported. Previously, we reported the vinyl modified BINAP ligand, (S)-5, 5-divinylBINAP. they were copolymerized with different monomers and a series of organic polymers with different pore structures were prepared. Its supported Rh-based catalysts showed higher enantioselectivity than homogeneous catalysts in asymmetric hydroformylation of styrene. In this paper, (S)-4,4-divinylBINAP ligands were synthesized by different bromination steps. The two chiral ligands with vinyl functional groups were copolymerized with divinylbenzene (DVB) in the same molar ratio to give two different organic polymers. After loading [RuCl_2 (benzene)] _ 2, we get Ru/4-BINAP@POPs and Ru/5-BINAP@POPs-1., respectively. The catalyst Ru/5-BINAP@POPs-2; was synthesized by one pot method. Ru/5-BINAP@POPs-3 and Ru/5-BINAP@POPs-4 catalysts were synthesized with [RuCl_2 (p-cyme)] 2 and RuCl_3, respectively. Ru/4-BINAP@POPs and Ru/5-BINAP@POPs-1 catalysts have similar pore structure. However, the mesoporous pore size of the Ru/5-BINAP@POPs-2 catalyst synthesized by the one-pot method is larger than that of the 5-BINAP@POPs polymer and the ~ (13) C NMR shows that both of the catalysts have obvious absorption peaks at 145137 and 128 ppm. It can be attributed to the peak of carbon vibration on naphthalene ring and benzene ring. The peak at 44.0 ppm belongs to the carbon vibrational peak on methylene, and the 31p NMR shows that P has not been oxidized in the polymer. The obtained Ru/POPs catalyst was applied to the heterogeneous asymmetric hydrogenation of methyl acetoacetate. The Ru/5-BINAP@POPs-1 catalyst had a faster reaction rate with Ru/4-BINAP@POPs. Under the same reaction conditions, the activity of the catalyst is Ru/5-BINAP@POPs-1Ru/5-BINAP@POPs-3Ru/5-BINAP@POPs-4Ru/5-BINAP@POPs-2.. In addition, Ru/5-BINAP@POPs-1 catalyst has good substrate adaptability to 尾-keto ester, and it can be reused for 6 times in the tank reaction, but the activity is almost unchanged. It was found that there was no obvious Ru / Ru bond in the catalyst before and after the catalyst was used. The results show that the Ru metal is highly dispersed on the catalyst and has high stability, and the metal is not easy to aggregate, which is also the reason for its high activity and stability.
【作者单位】： 中国科学院大连化学物理研究所洁净能源国家实验室(筹);中国科学院大学;厦门大学化学系;中国科学院上海应用物理研究所上海同步辐射中心;中国科学院大连化学物理研究所催化基础国家重点实验室;
【基金】：supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)~~
【分类号】：O621.251;O631
[Abstract]:Chiral porous organic polymers have high stability and catalytic activity and are widely used in heterogeneous asymmetric catalysis. At present, most of the studies are focused on the synthesis of polymers with microporous structure, but few reports of polymers with multiple pore structures (including mesoporous and microporous) have been reported. Previously, we reported the vinyl modified BINAP ligand, (S)-5, 5-divinylBINAP. they were copolymerized with different monomers and a series of organic polymers with different pore structures were prepared. Its supported Rh-based catalysts showed higher enantioselectivity than homogeneous catalysts in asymmetric hydroformylation of styrene. In this paper, (S)-4,4-divinylBINAP ligands were synthesized by different bromination steps. The two chiral ligands with vinyl functional groups were copolymerized with divinylbenzene (DVB) in the same molar ratio to give two different organic polymers. After loading [RuCl_2 (benzene)] _ 2, we get Ru/4-BINAP@POPs and Ru/5-BINAP@POPs-1., respectively. The catalyst Ru/5-BINAP@POPs-2; was synthesized by one pot method. Ru/5-BINAP@POPs-3 and Ru/5-BINAP@POPs-4 catalysts were synthesized with [RuCl_2 (p-cyme)] 2 and RuCl_3, respectively. Ru/4-BINAP@POPs and Ru/5-BINAP@POPs-1 catalysts have similar pore structure. However, the mesoporous pore size of the Ru/5-BINAP@POPs-2 catalyst synthesized by the one-pot method is larger than that of the 5-BINAP@POPs polymer and the ~ (13) C NMR shows that both of the catalysts have obvious absorption peaks at 145137 and 128 ppm. It can be attributed to the peak of carbon vibration on naphthalene ring and benzene ring. The peak at 44.0 ppm belongs to the carbon vibrational peak on methylene, and the 31p NMR shows that P has not been oxidized in the polymer. The obtained Ru/POPs catalyst was applied to the heterogeneous asymmetric hydrogenation of methyl acetoacetate. The Ru/5-BINAP@POPs-1 catalyst had a faster reaction rate with Ru/4-BINAP@POPs. Under the same reaction conditions, the activity of the catalyst is Ru/5-BINAP@POPs-1Ru/5-BINAP@POPs-3Ru/5-BINAP@POPs-4Ru/5-BINAP@POPs-2.. In addition, Ru/5-BINAP@POPs-1 catalyst has good substrate adaptability to 尾-keto ester, and it can be reused for 6 times in the tank reaction, but the activity is almost unchanged. It was found that there was no obvious Ru / Ru bond in the catalyst before and after the catalyst was used. The results show that the Ru metal is highly dispersed on the catalyst and has high stability, and the metal is not easy to aggregate, which is also the reason for its high activity and stability.
【作者单位】： 中国科学院大连化学物理研究所洁净能源国家实验室(筹);中国科学院大学;厦门大学化学系;中国科学院上海应用物理研究所上海同步辐射中心;中国科学院大连化学物理研究所催化基础国家重点实验室;
【基金】：supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)~~
【分类号】：O621.251;O631
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