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

doi:10.1016/S1872-2067(17)62826-2

催化学报 ›› 2017, Vol. 38 ›› Issue (5): 890-898.DOI: 10.1016/S1872-2067(17)62826-2

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

王涛^a,c, 吕元^a, 熊凯^d, 汪文龙^a, 张浩^e, 詹庄平^d, 姜政^e, 丁云杰^a,b

a. 中国科学院大连化学物理研究所洁净能源国家实验室(筹), 辽宁大连 116023;
b. 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, 辽宁大连 116023;
c. 中国科学院大学, 北京 100049;
d. 厦门大学化学系, 福建厦门 361005;
e. 中国科学院上海应用物理研究所上海同步辐射中心, 上海 201204

收稿日期:2017-02-22 修回日期:2017-03-23 出版日期:2017-05-18 发布日期:2017-05-10
通讯作者: Yunjie Ding, Yuan Lyu
基金资助:
中国科学院战略先导研究计划（XDB17020400）.

Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis

Tao Wang^a,c, Yuan Lyu^a, Kai Xiong^d, Wenlong Wang^a, Hao Zhang^e, Zhuangping Zhan^d, Zheng Jiang^e, Yunjie Ding^a,b

a. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b. State Key Laboratory of catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c. University of Chinese Academy of Sciences, Beijing 100049, China;
d. Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
e. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China

Received:2017-02-22 Revised:2017-03-23 Online:2017-05-18 Published:2017-05-10
Supported by:
This work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020400).

摘要/Abstract

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[RuCl₂（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[RuCl₂（p-cyme）]₂和RuCl₃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¹³C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-1>Ru/5-BINAP@POPs-3>Ru/5-BINAP@POPs-4>Ru/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.

关键词: (S)-4,4’-二乙烯基-BINAP, (S)-5,5’-二乙烯基-BINAP, 聚合物负载钌催化剂, 多相不对称加氢, β-酮酸酯

Abstract:

Two vinyl-functionalized chiral 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl (BINAP) ligands, (S)-4,4’-divinyl-BINAP and (S)-5,5’-divinyl-BINAP, were successfully synthesized. Chiral BINAP-based porous organic polymers (POPs), denoted as 4-BINAP@POPs and 5-BINAP@POPs, were efficiently prepared via the copolymerization of vinyl-functionalized BINAP with divinyl benzene under solvothermal conditions. Thorough characterization using nuclear magnetic resonance spectroscopy, thermogravimetric analysis, extended X-ray absorption fine structure analysis, and high-angle annular dark-field scanning transmission electron microscopy, we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores. Ru was introduced as a catalytic species into the POPs using different synthetic routes. Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation of β-keto esters revealed their excellent chiral inducibility as well as high activity and stability. Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.

Key words: (S)-4,4’-divinyl-BINAP, (S)-5,5’-divinyl-BINAP, Porous organic polymers supported, ruthenium, Heterogeneous asymmetric, hydrogenation, β-keto esters

王涛, 吕元, 熊凯, 汪文龙, 张浩, 詹庄平, 姜政, 丁云杰. 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[J]. 催化学报, 2017, 38(5): 890-898.

Tao Wang, Yuan Lyu, Kai Xiong, Wenlong Wang, Hao Zhang, Zhuangping Zhan, Zheng Jiang, Yunjie Ding. Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis[J]. Chinese Journal of Catalysis, 2017, 38(5): 890-898.

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参考文献

[1] A. G. Hu, H. L. Ngo, W. B. Lin, J. Am. Chem. Soc., 2003, 125, 11490–11491.
[2] C. D. Wu, A. G. Hu, L. Zhang, W. B. Lin, J. Am. Chem. Soc., 2005, 127, 8940–8941.
[3] H. B. Yu, Q. S. Hu, L. Pu, Tetrahedron Lett., 2000, 41, 1681–1685.
[4] Q. H. Fan, C. Y. Ren, C. H. Yeung, W. H. Hu, A. S. C. Chan, J. Am. Chem. Soc., 1999, 121, 7407–7408.
[5] Q. H. Fan, G. H. Liu, G. J. Deng, X. M. Chen, A. S. C. Chan, Tetrahedron Lett., 2001, 42, 9047–9050.
[6] S. Y. Ding, W. Wang, Chem. Soc. Rev., 2013, 42, 548–568.
[7] M. Pilaski, J. Artz, H. U. Islam, A. M. Beale, R. Palkovits, Microporous Mesoporous Mater., 2016, 227, 219–227.
[8] W. Y. Gao, M. Chrzanowski, S. Q. Ma, Chem. Soc. Rev., 2014, 43, 5841–5866.
[9] H. M. El-Kaderi, J. R. Hunt, J. L. Mendoza-Cortes, A. P. Cote, R. E. Taylor, M. O'Keeffe, O. M. Yaghi, Science, 2007, 316, 268–272.
[10] Y. G. Zhang, S. N. Riduan, Chem. Soc. Rev., 2012, 41, 2083–2094.
[11] S. Xu, Z. H. Weng, J. Tan, J. Guo, C. C. Wang, Polym. Chem., 2015, 6, 2892–2899.
[12] S. J. Kraft, G. H. Zhang, D. Childers, F. Dogan, J. T. Miller, S. T. Nguyen, A. S. Hock, Organometallics, 2014, 33, 2517–2522.
[13] W. L. Wang, A. M. Zheng, P. Q. Zhao, C. G. Xia, F. W. Li, ACS Catal., 2014, 4, 321–327.
[14] H. Y. Yang, M. H. Xu, Chin. J. Chem., 2013, 31, 119–122.
[15] Q. Sun, Z. F. Dai, X. J. Meng, F. S. Xiao, Chem. Soc. Rev., 2015, 44, 6018–6034.
[16] P. Kaur, J. T. Hupp, S. B. T. Nguyen, ACS Catal., 2011, 1, 819–835.
[17] T. Ohkuma, H. Takeno, Y. Honda, R. Noyori, Adv. Synth. Catal., 2001, 343, 369–375.
[18] L. Q. Ma, M. M. Wanderley, W. B. Lin, ACS Catal., 2011, 1, 691–697.
[19] W. K. An, M. Y. Han, C. A. Wang, S. M. Yu, Y. Zhang, S. Bai, W. Wang, Chem. Eur. J., 2014, 20, 11019–11028.
[20] D. S. Kundu, J. Schmidt, C. Bleschke, A. Thomas, S. Blechert, Angew. Chem. Int. Ed., 2012, 51, 5456–5459.
[21] J. Q. Dong, Y. Liu, Y. Cui, Chem. Commun., 2014, 50, 14949–14952.
[22] X. Wang, J. Li, S. M. Lu, Y. Liu, C. Li, Chin. J. Catal., 2015, 36, 1170–1174.
[23] Q. Sun, X. J. Meng, X. Liu, X. M. Zhang, Y. Yang, Q. H. Yang, F. S. Xiao, Chem. Commun., 2012, 48, 10505–10507.
[24] Q. Sun, Y. Y. Jin, L. F. Zhu, L. Wang, X. J. Meng, F. S. Xiao, Nano Today, 2013, 8, 342–350.
[25] C. Perego, R. Millini, Chem. Soc. Rev., 2013, 42, 3956–3976.
[26] A. Thomas, Angew. Chem. Int. Ed., 2010, 49, 8328–8344.
[27] Q. Sun, S. Q. Ma, Z. F. Dai, X. J. Meng, F. S. Xiao, J. Mater. Chem. A, 2015, 3, 23871–23875.
[28] X. M. Zhang, Y. P. Zhao, J. Peng, Q. H. Yang, Green Chem., 2015, 17, 1899–1906.
[29] A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T. Souchi, R. Noyori, J. Am. Chem. Soc., 1980, 102, 7932–7934.
[30] R. T. Halle, E. Schulz, M. Spagnol, M. Lemaire, Tetrahedron Lett., 2000, 41, 3323–3326.
[31] E. Framery, B. Andrioletti, M. Lemaire, Tetrahedron, 2010, 21, 1110–1124.
[32] C. Saluzzo, T. Lamouille, F. Le Guyader, M. Lemaire, Tetrahedron: Asymmetry, 2002, 13, 1141–1146.
[33] F. M. Bautista, V. Caballero, J. M. Campelo, D. Luna, J. M. Marinas, A. A. Romero, I. Romero, I. Serrano, A. Llobet, Top. Catal., 2006, 40, 193–205.
[34] T. Wang, Y. Lyu, X. K. Chen, C. Y. Li, M. Jiang, X. G. Song, Y. J. Ding, RSC Adv., 2016, 6, 28447–28450.
[35] Y. X. Liang, Q. Jing, X. Li, L. Shi, K. L. Ding, J. Am. Chem. Soc., 2005, 127, 7694–7695.
[36] J. K. Kassube, H. Wadepohl, L. H. Gade, Adv. Synth. Catal., 2009, 351, 607–616.
[37] P. Y. Wang, X. Liu, J. Yang, Y. Yang, L. Zhang, Q. H. Yang, C. Li, J. Mater. Chem., 2009, 19, 8009–8014.
[38] J. Peng, X. F. Wang, X. M. Zhang, S. Y. Bai, Y. P. Zhao, C. Li, Q. H. Yang, Catal. Sci. Technol., 2015, 5, 666–672.
[39] M. Jiang, L. Yan, X. P. Sun, R. H. Lin, X. G. Song, Z. Jiang, Y. J. Ding, React. Kinet. Mech. Catal., 2015, 116, 223–234.
[40] K. Abdur-Rashid, S. E. Clapham, A. Hadzovic, J. N. Harvey, A. J. Lough, R. H. Morris, J. Am. Chem. Soc., 2002, 124, 15104–15118.
[41] H. L. Ngo, A. G. Hu, W. B. Lin, Chem. Commun., 2003, 1912–1913.
[42] S. Maeda, K. Ohno, J. Am. Chem. Soc., 2008, 130, 17228–17229.
[43] Q. Sun, Z. F. Dai, X. L. Liu, N. Sheng, F. Deng, X. J. Meng, F. S. Xiao, J. Am. Chem. Soc., 2015, 137, 5204–5209.

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

Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis

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