A New Approach for Supramolecular Iminium Catalysis

doi:10.6023/A14040342

Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (7): 845-848.DOI: 10.6023/A14040342 Previous Articles Next Articles

Special Issue: 不对称催化与合成

Communication

超分子亚胺离子催化的新途径

于天洋, 王瑶, 许鹏飞

兰州大学功能有机分子化学国家重点实验室兰州 730000

投稿日期:2014-04-30 发布日期:2014-06-24
通讯作者: 许鹏飞 E-mail:xupf@lzu.edu.cn
基金资助:
项目受国家自然科学基金（No.21372105）、长江学者和创新团队发展计划（No.IRT1138）、国际科技合作计划（No.2013DFR70580）、国家重点基础研究发展计划（No.2010CB833203）和教育部“111”计划资助.

A New Approach for Supramolecular Iminium Catalysis

Yu Tianyang, Wang Yao, Xu Pengfei

State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China

Received:2014-04-30 Published:2014-06-24
Supported by:
Project supported by National Natural Science Foundation of China (No. 21372105), Program for Changjiang Scholars and Innovative Research Team in University (No. IRT1138), the International S&T Cooperation Program of China (No. 2013DFR70580), the National Basic Research Program of China (No. 2010CB833203), and the “111” Program from MOE of P.R. China.

1. A New Approach for Supramolecular Iminium Catalysis.PDF(2885KB)

Abstract

An alternative modular strategy has been developed for hydrogen-bond-mediated supramolecular iminium catalysis (SIC). To improve the efficiency of traditional iminium ion catalysis and provide a new approach to asymmetric catalysis, we recently developed a new concept which aims to activate iminium ions. To expand the scope of SIC, we reported here a rationally designed strategy involving the dual activation of both iminium ions and the nucleophilic partner that provides new opportunities for improving the reactivity and designing new reactions. We analyzed the different reaction rates of the addition reaction of malonate to α,β-unsaturated aldehyde catalyzed by traditional iminium ion catalysis and supramolecular iminium catalysis by the means of ¹H NMR monitoring of the reaction conversions and comparison of the isolated yields. Moreover, different carboxylic acids were employed in iminium catalytic Michael addition reaction of malonate to α,β-unsaturated aldehyde to test our hypothesis. General speaking, by using this novel supramolecular iminium catalysis, the enantioselectivities of the Michael addition products are excellent (93%～95%) with moderate to good yields (61%～86%), meanwhile, all these reactions were rather slow and only 33%～57% conversions were obtained even after 7 days in the presence of traditional iminium ion catalysis. Further reducing the catalyst loading to 5 mol%, the reaction proceeded smoothly to give a >90% conversion with 94% ee after 12 h. The results revealed that the use of less acidic acid which generates lower concentration of iminium ion associated with stronger anion-binding stabilized conjugate base gives faster reaction rate. The experimental results indicate a new approach for SIC which involves an anion-exchange process between anion-binding stabilized carboxylate ion and malonate. The self-assembled supramolecular system has higher reactivity, better efficiency and greater turnover numbers. This general strategy has the potential to be applied in many iminium catalytic nucleophilic addition reactions and might provide new opportunities for designing new asymmetric reactions. The further study is currently underway in our laboratory.

Key words: asymmetric catalysis, supramolecular iminium catalysis, organocatalysis, supramolecular chemistry, addition reaction

Cite this article

Yu Tianyang, Wang Yao, Xu Pengfei. A New Approach for Supramolecular Iminium Catalysis[J]. Acta Chimica Sinica, 2014, 72(7): 845-848.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Wang, H.; He, Q.; Tan, K. Acta Chim. Sinica 2013, 71, 1663. (王红, 何桥, 谭凯, 化学学报, 2013, 71, 1663.);
(b) Chen, C.; Zhan, E.; Li, Y.; Shen, W. Acta Chim. Sinica 2013, 71, 1505. (陈春辉, 展恩胜, 李勇, 申文杰, 化学学报, 2013, 71, 1505.);
(c) Du, L.; Cao, P.; Liao, J. Acta Chim. Sinica 2013, 71, 1239. (杜乐, 曹鹏, 廖建, 化学学报, 2013, 71, 1239.);
(d) Ma, F.; Chen, J. Acta Chim. Sinica 2013, 71, 1118. (马菲, 陈建新, 化学学报, 2013, 71, 1118.);
(e) Wu, X.; Li, M.; Gong, L. Acta Chim. Sinica 2013, 71, 1091. (吴祥, 李明丽, 龚流柱, 化学学报, 2013, 71, 1091.);
(f) Hu, R.; Zhang, C.; Pei, Z. Acta Chim. Sinica 2013, 71, 1064. (胡锐, 张承平, 裴志胜, 化学学报, 2013, 71, 1064.);
(g) Huang, J.; Luo, S.; Gong, L. Acta Chim. Sinica 2013, 71, 879. (黄建洲, 罗时玮, 龚流柱, 化学学报, 2013, 71, 879.);
(h) He, Z.; Huang, Y.; Verpoort, F. Acta Chim. Sinica 2013, 71, 700. (何展荣, 黄毅勇, Verpoort Francis, 化学学报, 2013, 71, 700.);
(i) Ma, B.; Deng, G.; Liu, J.; He, Y.; Fan, Q. Acta Chim. Sinica 2013, 71, 528. (马保德, 邓国军, 刘继, 何艳梅, 范青华, 化学学报, 2013, 71, 528.);
(j) Qiu, H.; Zhang, D.; Liu, S.; Qiu, L.; Zhou, J.; Qian, Y.; Zhai, C.; Hu, W. Acta Chim. Sinica 2012, 70, 2484. (邱晃, 张丹, 刘顺英, 邱林, 周俊, 钱宇, 翟昌伟, 胡文浩, 化学学报, 2012, 70, 2484.);
(k) Zheng, K.; Lin, L.; Feng, X. Acta Chim. Sinica 2012, 70, 1785. (郑柯, 林丽丽, 冯小明, 化学学报, 2012, 70, 1785.);
(l) Sun, X.; Peng, J.; Zhang, S.; Zhou, Q.; Dong, L.; Chen, Y. Acta Chim. Sinica 2012, 70, 1682. (孙峋皓, 彭景, 张叔阳, 周清清, 董琳, 陈应春, 化学学报, 2012, 70, 1682.);
(m) Lv, J.; Zhong, X.; Cheng, J.-P.; Luo, S. Acta Chim. Sinica 2012, 70, 1518. (吕健, 钟兴仁, 程津培, 罗三中, 化学学报, 2012, 70, 1518.);
(n) Liu, Y.; Wang, Z.; Ding, K. Acta Chim. Sinica 2012, 70, 1464. (刘龑, 王正, 丁奎岭, 化学学报, 2012, 70, 1464.);
(o) Liu, Y.; Zhou, J. Acta Chim. Sinica 2012, 70, 1451. (刘运林, 周剑, 化学学报, 2012, 70, 1451.);
(p) Xie, J.; Zhou, Q. Acta Chim. Sinica 2012, 70, 1427. (谢建华, 周其林, 化学学报, 2012, 70, 1427.)

[2] Vogl, E. M.; Gröger, H.; Shibasaki, M. Angew. Chem., Int. Ed. 1999, 38, 1570.

[3] For selected reviews, see: (a) Lelais, G.; MacMillan, D. W. C. Aldrichim. Acta 2006, 39, 79;
(b) List, B. Chem. Commun. 2006, 819;
(c) Dalko, P. I. Enantioselective Organocatalysis, Wiley-VCH, Weinheim, 2007;
(d) Erkkilä, A.; Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416;
(e) Dondoni, A.; Massi, A. Angew. Chem. Int. Ed. 2008, 47, 4638;
(f) MacMillan, D. W. C. Nature 2008, 455, 304;
(g) Melchiorre, P.; Marigo, M.; Carlone, A.; Bartoli, G. Angew. Chem. Int. Ed. 2008, 47, 6138;
(h) Bertelsen, S.; Jørgensen, K. A. Chem. Soc. Rev. 2009, 38, 2178;
(i) Marqués-López, E.; Herrerabc, R. P.; Christmann, M. Nat. Prod. Rep. 2010, 27, 1138;
(j) Grondal1, C.; Jeanty, M.; Enders, D. Nat. Chem. 2010, 2, 167;
(k) Nielsen, M.; Worgull, D.; Zweifel, T.; Gschwend, B.; Bertelsen, S.; Jørgensen, K. A. Chem. Commun. 2011, 47, 632.

[4] Wang, Y.; Yu, T.-Y.; Zhang, H.-B.; Luo, Y.-C.; Xu, P.-F. Angew. Chem., Int. Ed. 2012, 51, 12339.

[5] For selected reviews on anion-binding chemistry, see: (a) Caltagirone, C.; Gale, P. A. Chem. Soc. Rev. 2009, 38, 520;
(b) Kubik, S. Chem. Soc. Rev. 2009, 38, 585;
(c) Zhang, Z.; Schreiner, P. R. Chem. Soc. Rev. 2009, 38, 1187. For selected examples of thiourea anion-binding catalysis, see:
(d) Kotke, M.; Schreiner, P. R. Tetrahedron 2006, 62, 434;
(e) Kotke, M.; Schreiner, P. R. Synthesis 2007, 779;
(f) Raheem, I. T.; Thiara, P. S.; Peterson, E. A.; Jacobsen, E. N. J. Am. Chem. Soc. 2007, 129, 13404;
(g) Reisman, S. E.; Doyle, A. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2008, 130, 7198;
(h) De, C. K.; Klauber, E. G.; Seidel, D. J. Am. Chem. Soc. 2009, 131, 17060;
(i) Zuend, S. J.; Coughlin, M. P.; Lalonde, M. P.; Jacobsen, E. N. Nature 2009, 461, 968;
(j) Xu, H.; Zuend, S. J.; Woll, M. G.; Tao, Y.; Jacobsen, E. N. Science 2010, 327, 986;
(k) Brown, A. R.; Kuo, W.-H.; Jacobsen, E. N. J. Am. Chem. Soc. 2010, 132, 9286;
(l) Singh, R. P.; Foxman, B. M.; Deng, L. J. Am. Chem. Soc. 2010, 132, 9558;
(m) Klauber, E. G.; De, C. K.; Shah, T. K.; Seidel, D. J. Am. Chem. Soc. 2010, 132, 13624;
(n) Birrell, J. A.; Desrosiers, J.-N.; Jacobsen, E. N. J. Am. Chem. Soc. 2011, 133, 13872;
(o) Burns, N. Z.; Witten, M. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2011, 133, 14578;
(p) Zhu, R.-X.; Zhang, D.-J.; Wang, R.-X.; Liu, C.-B. Acta Chim. Sinica 2008, 66, 885. (朱荣秀, 张冬菊, 王若曦, 刘成卜, 化学学报, 2008, 66, 885.);
(q) Zhu, Y.; Zhang, X.; Zhang, Q.; Dai, X.; Wu, J. Acta Chim. Sinica 2011, 69, 709. (朱玉莲, 张小燕, 张岐, 戴雪芹, 吴静波, 化学学报, 2011, 69, 709.)

[6] (a) Brandau, S.; Landa, A.; Franzen, J.; Marigo, M.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2006, 45, 4305;
(b) Wang, Y. C.; Li, P. F.; Liang, X. M.; Ye, J. X. Adv. Synth. Catal. 2008, 350, 1383.

[7] Bwdwell, F. G.; Algrim, D. J. Org. Chem. 1976, 41, 2507.

[1]	Zhanglong Yu, Zhongliang Li, Changjiang Yang, Qiangshuai Gu, Xinyuan Liu. Research Progress on Copper-Catalyzed Enantioselective Desymmetrization of Diols^★ [J]. Acta Chimica Sinica, 2023, 81(8): 955-966.
[2]	Shuang Yang, Ningyi Wang, Qingqing Hang, Yuchen Zhang, Feng Shi. Advances in Catalytic Asymmetric Reactions Involving o-Hydroxyphenyl Substituted p-Quinone Methides^★ [J]. Acta Chimica Sinica, 2023, 81(7): 793-808.
[3]	Wang Rui-Xiang, Zhao Qing-Ru, Gu Qing, You Shu-Li. Gold/Iridium Catalyzed Alkynylamide Cyclization/Asymmetric Allylic Benzylation Cascade Reaction^★ [J]. Acta Chimica Sinica, 2023, 81(5): 431-434.
[4]	Qingduan Meng, Jiahong Han, Yixiao Pan, Wei Hao, Qing-Hua Fan. Asymmetric Synthesis of C₁-Symmetric Chiral N-Heterocyclic Carbene (NHC) Ligands and Their Applications in Asymmetric Catalysis^★ [J]. Acta Chimica Sinica, 2023, 81(10): 1271-1279.
[5]	Xiaochen Wang, Zeyao Ji, Jian Liu, Bingfu Wang, Hui Jin, Lixin Zhang. Advances in Organocatalytic Asymmetric Reactions Involving Thioesters [J]. Acta Chimica Sinica, 2023, 81(1): 64-83.
[6]	Lai Zhang, Jian Xiao, Yawen Wang, Yu Peng. Recent Advances on the Construction of Chiral Dihydrobenzofurans by Asymmetric [3+2] Cyclization Reactions of Phenols (Quinones) and Alkenes [J]. Acta Chimica Sinica, 2022, 80(8): 1152-1164.
[7]	Jinyue Ma, Lufei Huang, Baowen Zhou, Lin Yao. Construction and Catalysis Advances of Inorganic Chiral Nanostructures [J]. Acta Chimica Sinica, 2022, 80(11): 1507-1523.
[8]	Qing-Ru Zhao, Ru Jiang, Shu-Li You. Ir-catalyzed Sequential Asymmetric Allylic Substitution/Olefin Isomerization for the Synthesis of Axially Chiral Compounds [J]. Acta Chimica Sinica, 2021, 79(9): 1107-1112.
[9]	Bo-Shuai Mu, Zhi-Hao Zhang, Wen-Biao Wu, Jin-Sheng Yu, Jian Zhou. Recent Advances in Synthesis of Chiral 1,2-Dihydropyridines [J]. Acta Chimica Sinica, 2021, 79(6): 685-693.
[10]	Yi Li, Ming-Hua Xu. Applications of Asymmetric Petasis Reaction in the Synthesis of Chiral Amines [J]. Acta Chimica Sinica, 2021, 79(11): 1345-1359.
[11]	Chen Yougen, Ding Yuansheng. Recent Progress of Organocatalyzed Group Transfer Polymerization [J]. Acta Chimica Sinica, 2020, 78(8): 733-745.
[12]	Cheng Lei, Zhou Qilin. Advances on Nickel-Catalyzed C(sp³)-C(sp³) Bond Formation [J]. Acta Chimica Sinica, 2020, 78(10): 1017-1029.
[13]	Wang Qiang, Gu Qing, You Shu-Li. Recent Progress on Transition-Metal-Catalyzed Asymmetric C-H Bond Functionalization for the Synthesis of Biaryl Atropisomers [J]. Acta Chim. Sinica, 2019, 77(8): 690-704.
[14]	Chen Zhiyao, Liu Jiewei, Cui Hao, Zhang Li, Su Chengyong. Applications of Porphyrin Metal-Organic Frameworks in CO₂ Capture and Conversion [J]. Acta Chim. Sinica, 2019, 77(3): 242-252.
[15]	Zhou Yuanchun, Zhou Zhi, Du Wei, Chen Yingchun. Asymmetric Inverse-Electron-Demand Diels-Alder Reaction of 2-Pyrone and 2,5-Dienones via HOMO-Activation [J]. Acta Chim. Sinica, 2018, 76(5): 382-386.

超分子亚胺离子催化的新途径

A New Approach for Supramolecular Iminium Catalysis

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments