树状分子BINAP膦配体的合成及其在不对称氢化中的应用: 结构与性能关系探究

doi:10.6023/A13010156

化学学报 ›› 2013, Vol. 71 ›› Issue (04): 528-534.DOI: 10.6023/A13010156 上一篇下一篇

研究论文

树状分子BINAP膦配体的合成及其在不对称氢化中的应用: 结构与性能关系探究

马保德^a, 邓国军^b, 刘继^a, 何艳梅^a, 范青华^a

a 中国科学院化学研究所中国科学院分子识别与功能重点实验室北京分子科学国家实验室北京 100190;
b 湘潭大学化学学院环境友好化学与应用教育部重点实验室湘潭 411105

投稿日期:2013-01-31 发布日期:2013-02-20
通讯作者: 范青华 E-mail:fanqh@iccas.ac.cn
基金资助:
项目受国家自然科学基金(No. 21232008)、国家重点基础研究发展计划(973 计划) (No. 2010CB833300)资助.

Synthesis of Dendritic BINAP Ligands and Their Applications in the Asymmetric Hydrogenation: Exploring the Relationship between Catalyst Structure and Catalytic Performance

Ma Baode^a, Deng Guojun^b, Liu Ji^a, He Yanmei^a, Fan Qinghua^a

a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190;
b Key Laboratory for Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105

Received:2013-01-31 Published:2013-02-20
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21232008), the National Basic Research Program of China (973 Program) (No. 2010CB833300).

文章分享

1. 树状分子BINAP膦配体的合成及其在不对称氢化中的应用: 结构与性能关系探究.PDF(1072KB)

摘要/Abstract

设计并合成了系列具有不同代数以及不同结构的手性树状分子BINAP配体. 以Ru-催化的2-芳基丙烯酸的不对称氢化和Rh-催化的乙酰氨基肉桂酸的不对称氢化为模型反应, 结合圆二色谱分析方法, 系统研究了树状分子催化剂的结构与催化性能的关系. 在2-芳基丙烯酸的不对称氢化中, 发现双边取代的树状分子催化剂表现出明显高于小分子催化剂的催化活性, 反应速度随着树状分子代数的增加而加快, 当反应溶剂由甲苯/甲醇(1∶1, V/V)变为纯甲苯时, 这种树状分子加速效应更加明显; 而单边取代的树状分子催化剂, 由于催化活性中心远离树状分子载体, 因此其催化活性与小分子催化剂几乎相同. 此外, 圆二色(CD)谱研究表明, 双边取代的树状分子配体有不同于单边取代树状分子配体和小分子BINAP配体的Cotton效应, 说明树状分子的引入可能影响到位于其核心的手性配体的微环境. 这些结果显示树状分子载体在催化活性中心周围所构筑的微环境在促进催化剂活性中发挥了关键作用. 这种“微环境效应”还在脱氢氨基酸的不对称氢化中得到了进一步证明. 最后, 通过溶剂沉淀法, 实现了树状分子催化剂与产物的方便分离, 催化剂至少可以回收使用三次, 其催化活性和对映选择性没有任何降低.

关键词: 树状催化剂, 手性膦配体, 不对称氢化, 树状分子效应, 负载

Series of chiral dendritic BINAP ligands of different generations and with varied structures have been designed and synthesized through incorporation of BINAP unit into the core (disubstituted ligand) or the focal point (monosubstituted ligand) of the Fréchet’s polyether dendrimers. The relationship between catalyst structure and catalytic behavior was explored by choosing the Ru-catalyzed asymmetric hydrogenation of 2-aryl acrylic acid and Rh-catalyzed asymmetric hydrogenation of acetamidocinnamic acid as model reactions together with CD spectra analysis. It was found that the disubstituted dendritic catalysts showed obvious higher activity than the small molecular catalyst, and the reaction rate increased with the increase of the generation. This rate enhancement became more significant when changing the solvent from toluene/methanol (1/1, V/V) to neat toluene. While the monosubstituted dendritic catalysts showed similar performance with the small molecular catalyst, which was due to that the catalytic center located away from the dendritic support. In addition, the disubstituted dendritic BINAP ligands showed different Cotton effect in CD spectra with regard to the monosubstituted dendritic BINAP ligands and BINAP itself, suggesting that the microenvironment inside the disubstituted BINAP-cored dendrimer might be influenced by the sterically demanding dendritic wedges. These results indicated that the microenvironment around the catalytic center created by the dendritic support played an important role in promoting catalytic activity. This positive dendritic effect was further observed in the Rh-catalyzed asymmetric hydrogenation of acetamidocinnamic acid. Finally, the dendritic catalyst could be easily recycled by solvent precipitation at least three times without any loss of activity and selectivity.

Key words: dendritic catalyst, chiral phosphine ligands, asymmetric hydrogenation, dendritic effect, immobilization ester

引用此文

马保德, 邓国军, 刘继, 何艳梅, 范青华. 树状分子BINAP膦配体的合成及其在不对称氢化中的应用: 结构与性能关系探究[J]. 化学学报, 2013, 71(04): 528-534.

Ma Baode, Deng Guojun, Liu Ji, He Yanmei, Fan Qinghua. Synthesis of Dendritic BINAP Ligands and Their Applications in the Asymmetric Hydrogenation: Exploring the Relationship between Catalyst Structure and Catalytic Performance[J]. Acta Chimica Sinica, 2013, 71(04): 528-534.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] For selected reviews, see: (a) Oosterom, G. E.; Reek, J. N. H.; Kamer, P. C. J.; van Leeuwen, P. W. N. M. Angew. Chem., Int. Ed. 2001, 40, 1828; (b) Astruc, D.; Chardac, F. Chem. Rev. 2001, 101, 2991; (c) van Heerbeek, R.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Reek, J. N. H. Chem. Rev. 2002, 102, 3717; (d) Fan, Q.-H.; Li, Y.-M.; Chan, A. S. C. Chem. Rev. 2002, 102, 3385.

[2] Knapen, J. W. J.; van der Made, A. W.; de Wilde, J. C.; van Leeuwen, P. W. N. M.; Wijkens, P.; Grove, D. M.; van Koten, G. Nature 1994, 372, 659.

[3] For selected reviews on chiral dendritic catalysts, see: (a) Seebach, D.; Rheiner, P. B.; Greiveldinger, G.; Butz, T.; Sellner, H. Top. Curr. Chem. 1998, 197, 125; (b) Kassube, J. K.; Gade, L. H. Top. Organomet. Chem. 2006, 20, 61; (c) Fan, Q.-H.; Deng, G.-J.; Feng, Y.; He, Y.-M. In Handbook of Asymmetric Heterogeneous Catalysis, Eds.: Ding, K.; Uozumi, Y., Wiley-VCH, Weinheim, 2008, p. 131; (d) Caminade, A. M.; Servin, P.; Laurent, R.; Majoral, J. P. Chem. Soc. Rev. 2008, 37, 56; (e) Ma, B.-D.; Fan, Q.-H. Sci. Sinica Chim. 2010, 40, 827.

[4] For reviews on dendritic effect in catalytic reactions, see: (a) Chow, H.-F.; Leung, C.-F.; Wang, G.; Yang, Y. Y. C. R. Chem. 2003, 6, 735; (b) Helms, B.; Fréchet, J. M. J. Adv. Synth. Catal. 2006, 348, 1125; (c) Fan, Q.-H.; Ding, K.-L. Top. Organomet. Chem. 2011, 36, 207.

[5] For selected examples of chiral dendrimer catalysts with positive dendritic effect, see: (a) Breinbauer, R.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2000, 39, 3604; (b) Ribourdouille, Y.; Engel, G. D.;Richard-Plouet, M.; Gade, L. H. Chem. Commun. 2003, 1228; (c) Fan, Q.-H.; Chen, Y.-M.; Chen, X.-M.; Jiang, D.-Z.; Xi, F.; Chan, A. S. C. Chem. Commun. 2000, 789; (d) Wang, Z.-J.; Deng, G.-J.; Li, Y.; He, Y.-M.; Tang, W.-J.; Fan, Q.-H. Org. Lett. 2007, 9, 1243; (e) Zhang, F.; Li, Y.; Li, Z.-W.; He, Y.-M.; Zhu, S.-F.; Fan, Q.-H.; Zhou, Q.-L. Chem. Commun. 2008, 6048; (f) Mitsui, K.; Hyatt, S. A.; Turner, D. A.; Hadad, C. M.; Parquette, J. R. Chem. Commun. 2009, 3261; (g) Kehat, T.; Portnoy, M. Chem. Commun. 2007, 2823; (h) Kassube, J. K.; Wadepohl, H.; Gade, L. H. Adv. Synth. Catal. 2009, 351, 607; (i) Gissibl, A.; Padié, C.; Hager, M.; Jaroschik, F.; Rasappan, R.; Cuevas-Yaňez, E.; Turrin, C. O.; Caminade, A. M.; Majoral, J. P.; Reiser, O. Org. Lett. 2007, 9, 2895; (j) Garcia, L.;Roglans, A.; Laurent, R.; Majoral, J. P.; Pla-Quintana, A.; Caminade, A. M. Chem. Commun. 2012, 48, 9248.

[6] (a) Deng, G.-J.; Fan, Q.-H.; Chen, X.-M. Chin. J. Chem. 2002, 20, 1139; (b) Deng, G.-J.; Fan, Q.-H.; Chen, X.-M.; Liu, D.-S.; Chan, A. S. C. Chem. Commun. 2002, 1570; (c) Deng, G.-J.; Fan, Q.-H.; Chen, X.-M.; Liu, G.-H. J. Mol. Catal. A 2003, 193, 21; (d) Yi, B.; Fan, Q.-H.; Deng, G.-J.; Li, Y.-M.; Qiu, L.-Q.; Chan, A. S. C. Org. Lett. 2004, 6, 1361; (e) Huang, Y.-Y.; He, Y.-M.; Zhou, H.-F.; Wu, L.; Li, B.-L.; Fan, Q. H. J. Org. Chem. 2006, 71, 2874; (f) Tang, W.-J.; Huang, Y.-Y.; He, Y.-M.; Fan, Q.-H. Tetrahedron: Asymmetry 2006, 17, 536; (g) Deng, G.-J.; Li, G.-R.; Zhu, L.-Y.; Zhou, H.-F.; He, Y.-M.; Fan, Q.-H.; Shuai, Z.-G. J. Mol. Catal. A 2006, 244, 118; (h) Li, Y.; He, Y.-M.; Li, Z.-W.; Zhang, F.; Fan, Q.-H. Org. Biomol. Chem. 2009, 7, 1890; (i) Liu, J.; Feng, Y.; Ma, B.-D.; He, Y.-M.; Fan, Q.-H. Eur. J. Org. Chem. 2012, 6737.

[7] Fan, Q.-H.; Hu, W.-H.; Ren, C.-Y.; Yeung, C. H.; Chan, A. S. C. J. Am. Chem. Soc. 1999, 121, 7407.

[8] Hawker, C. J.; Fréchet, J. M. J. J. Am. Chem. Soc. 1990, 112, 7638.

[9] Harrington, P. J.; Lodewijk, E. Org. Process Res. Dev. 1997, 1, 72.

[10] Ohta, T.; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R. J. Org. Chem. 1987, 52, 3174.

[11] Niu, Y.-H.; Yeung, L. K.; Crooks, R. M. J. Am. Chem. Soc. 2001, 123, 6840.

[12] (a) Dang, T.-P.; Kagan, H. B. J. Chem. Soc., Chem. Commun. 1971, 481; (b) Miyashita, A.; Yasuda, A.; Takaya, H.; Toriumi, K.; Ito, T.; Souchi, T.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 7932.

[1]	付信朴, 王秀玲, 王伟伟, 司锐, 贾春江. 团簇Au/CeO₂的制备及其催化CO氧化反应构效关系的研究^★[J]. 化学学报, 2023, 81(8): 874-883.
[2]	蔡新红, 陈建中, 张万斌. 镍催化不对称氢化构建手性C—X键的研究进展^★[J]. 化学学报, 2023, 81(6): 646-656.
[3]	张谭, 余钟亮, 余嘉祺, 万慧凝, 包成宇, 涂文强, 杨颂. 基于高性能负载型钼基载氮体的化学链合成氨性能研究[J]. 化学学报, 2022, 80(6): 788-796.
[4]	陈敬煌, 孟天, 武烈, 石恒冲, 杨帆, 孙健, 杨秀荣. AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究^※[J]. 化学学报, 2022, 80(2): 110-115.
[5]	马智烨, 叶丽, 吴雨桓, 赵彤. B,N-SnO₂/TiO₂光催化剂的制备及其光催化性能研究[J]. 化学学报, 2021, 79(9): 1173-1179.
[6]	余俊, 杨宇森, 卫敏. 水滑石基负载型催化剂的制备及其在催化反应中的应用[J]. 化学学报, 2019, 77(11): 1129-1139.
[7]	胡书博, 陈木旺, 翟小勇, 周永贵. 不对称氢化杂环亚胺合成四氢吡咯/吲哚[1,2-a]并吡嗪[J]. 化学学报, 2018, 76(2): 103-106.
[8]	冯爱虎, 于洋, 于云, 宋力昕. 沸石分子筛及其负载型催化剂去除VOCs研究进展[J]. 化学学报, 2018, 76(10): 757-773.
[9]	易云强, 吴娟, 方战强. 天然有机质在生物炭负载纳米镍铁降解十溴联苯醚过程中的影响作用机理辨识[J]. 化学学报, 2017, 75(6): 629-636.
[10]	袁珮, 陈建, 潘登, 鲍晓军. 聚苯乙烯非均相催化加氢吸附动力学及反应动力学研究[J]. 化学学报, 2016, 74(7): 603-611.
[11]	季益刚, 吴磊, 范青华. 金属/金属氧化物纳米粒子在不对称氢化和氢转移反应中的应用研究进展[J]. 化学学报, 2014, 72(7): 798-808.
[12]	刘勇兵, 杜海峰. “受阻路易斯酸碱对”催化的不对称氢化反应[J]. 化学学报, 2014, 72(7): 771-777.
[13]	陈春辉, 展恩胜, 李勇, 申文杰. α,β-不饱和酸多相不对称氢化反应中的钯粒径和载体酸性效应[J]. 化学学报, 2013, 71(11): 1505-1510.
[14]	崔光, 付云飞, 罗军, 刘培生, 丁爱中. 氧化铝负载多孔沸石球的制备及其在As 吸收中的应用[J]. 化学学报, 2012, 70(9): 1059-1065.
[15]	谢建华, 周其林. 金属催化的不对称氢化反应研究进展与展望[J]. 化学学报, 2012, 70(13): 1427-1438.

树状分子BINAP膦配体的合成及其在不对称氢化中的应用: 结构与性能关系探究

Synthesis of Dendritic BINAP Ligands and Their Applications in the Asymmetric Hydrogenation: Exploring the Relationship between Catalyst Structure and Catalytic Performance

PDF

补充材料

可视化

被引次数

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价