A Study on C—H Carboxylation Reaction of Terminal Alkynes with CO2 in Supercritical CO2

doi:10.6023/cjoc201403064

Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (10): 2172-2177.DOI: 10.6023/cjoc201403064 Previous Articles Next Articles

Notes

超临界二氧化碳介质中端炔C—H键与CO₂的羧化反应研究

李发旺^a,b, 索全伶^a, 洪海龙^a, 竺宁^a, 王亚琦^a, 韩利民^a

a. 内蒙古工业大学化工学院呼和浩特 010051;
b. 内蒙古化工职业学院化学工程系呼和浩特 010070

收稿日期:2014-03-29 修回日期:2014-05-16 发布日期:2014-06-03
通讯作者: 索全伶, 韩利民 E-mail:szj010062@163.com
基金资助:
国家自然科学基金（Nos. 21266019，21062011，21362019）资助项目.

A Study on C—H Carboxylation Reaction of Terminal Alkynes with CO₂in Supercritical CO₂

Li Fawang^a,b, Suo Quanling^a, Hong Hailong^a, Zhu Ning^a, Wang Yaqi^a, Han Limin^a

a. Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051;
b. Department of Chemical Engineering, Inner Mongolia Vocational College of Chemical Engineering, Huhhot 010070

Received:2014-03-29 Revised:2014-05-16 Published:2014-06-03
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21266019, 21062011, 21362019).

1. A Study on C—H Carboxylation Reaction of Terminal Alkynes with CO₂in Supercritical CO₂.PDF(688KB)

Abstract

A organic solvent free, new carboxylation pathway for C—H bond of terminal alkynes with supercritical CO₂ (ScCO₂) has been developed by using Ag(I)/DBU (1,8-diazabicyclo(5.4.0)undec-7-ene) catalytic system to obtain propiolic acid products with excellent yields in this work. In our reaction system, ScCO₂ not only acts as reactive solvent but also as reactant. DBU plays the roles of co-catalyst, nucleophile and base, and obviously enhances the reaction rate in ScCO₂. The Ag(I)/DBU catalytic system exhibits higher activity and wide substrate scope. Notably, both liquid and solid terminal alkynes can smoothly react with ScCO₂ to produce desired product. The reaction pathway of functionalized propiolic acid formation from the carboxylation of terminal alkynes with CO₂ is environment-friendly, simple, and economic.

Key words: AgOAc, DBU, terminal alkyne, ScCO₂, carboxylation

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Li Fawang, Suo Quanling, Hong Hailong, Zhu Ning, Wang Yaqi, Han Limin. A Study on C—H Carboxylation Reaction of Terminal Alkynes with CO₂in Supercritical CO₂[J]. Chin. J. Org. Chem., 2014, 34(10): 2172-2177.

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[1] (a) Lehmann, F.; Lake, L.; Currier, E. A.; Olsson, R.; Hacksell, U.; Luthman K. Eur. J. Med. Chem. 2007, 42, 276.
(b) Ho, Y.-S.; Duh, J.-S.; Jeng, J.-H.; Wang, Y.-J.; Liang, Y.-C.; Lin, C.-H.; Tseng, C.-J.; Yu, C.-F.; Chen, R.-J.; Lin, J.-K. Int. J. Cancer 2001, 91, 393.
(c) Dong, Y.; Guo, X.-Y.; Yu, Y.-Y.; Liu, G. Mol. Diversity 2013, 17, 1.
(d) Jiang, Y.-B.; Han, C.-M.; Liang, X.-Q.; Yang, P.; Wang, H. Chin. J. Org. Chem. 2012, 32, 1884 (in Chinese).
(江玉波, 韩春美, 梁雪秋, 杨朋, 王红, 有机化学, 2012, 32, 1884.)
[2] (a) Moon, J.; Jeong, M.; Nam, H.; Ju, J.; Moon, J. H.; Jung, H. M.; Lee, S. Org. Lett. 2008, 10, 945.
(b) Li, Y.; Jardine, K. J.; Tan, R.; Song, D.; Dong, V. M. Angew. Chem., Int. Ed. 2009, 121, 9870.
(c) Bararjanian, M.; Balalaie, S.; Rominger, F.; Movassagh, B.; Bijanzadeh, H. R. J. Org. Chem. 2010, 75, 2806.
(d) Feng, H.; Ermolat'ev, D. S.; Song, G.; Van der Eycken, E. V. Adv. Synth. Catal. 2012, 354, 505.
(e) He, Z.-B.; Zhang, R.; Hu, M.-Y.; Li, L.-C.; Ni, C.-F.; Hu, J.-B. Chem. Sci. 2013, 4, 3478.
[3] Arndt, M.; Risto, E.; Krause, T.; Gooßen, L. J. ChemCatChem 2012, 4, 484.
[4] (a) Omae, I. Coord. Chem. Rev. 2012, 256, 1384.
(b) Cokoja, M.; Bruckmeier, C.; Rieger, B.; Herrmann, W. A.; Kühn, F. E. Angew. Chem., Int. Ed. 2011, 50, 8510.
(c) Tsuji, Y.; Fujihara, T. Chem. Commun. 2012, 48, 9956.
(d) Yang, Z.-Z.; He, L.-N.; Gao, J.; Liu, A.-H.; Yu, B. Energy Environ. Sci. 2012, 5, 6602.
(f) Huang, K.; Sun, C.-L.; Shi, Z.-J. Chem. Soc. Rev. 2011, 40, 2435.
[5] (a) Sakakura, T.; Choi, J.-C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
(b) Sakakura, T.; Kohon, K. Chem. Commun. 2009, 1312.
(c) Mikkelsen, M.; Jørgensena, M.; Krebs, F. C. Energy Environ. Sci. 2010, 3, 43.
(d) Huang, K.; Sun, C.-L.; Shi, Z.-J. Chem. Soc. Rev. 2011, 40, 2435.
(e) Izumi, Y. Coord. Chem. Rev. 2013, 257, 171.
(f) Wang, H.-Y.; Xu, J.-F.; Jing, H.; Zhang, J.; Li, P.-Q.; Lu, F.-S. Acta Chim. Sinica 2013, 71, 941 (in Chinese).
(王祜英, 徐金凤, 井华, 张军, 李培强, 路福绥, 化学学报, 2013, 71, 941.)
[6] (a) Shi, M.; Nicholas, M. J. Am. Chem. Soc. 1997, 119, 5057.
(b) Johansson, R.; Wendt, O. F. Dalton Trans. 2007, 488.
(c) Wu, J.-G.; Hazari, N. Chem. Commun. 2011, 47, 1069.
[7] (a) Yeung, C. S.; Dong, V. M. J. Am. Chem. Soc. 2008, 130, 7826.
(b) Ochiai, H.; Jang, M.; Hirano, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2008, 10, 2681.
(c) Kobayashi, K.; Kondo, Y. Org. Lett. 2009, 11, 2035.
(d) Correa, A.; Martín, R. Angew. Chem., Int. Ed. 2009, 48, 6201.
[8] (a) Ohishi, T.; Nishiura, M.; Hou, Z. Angew. Chem., Int. Ed. 2008, 47, 5792.
(b) Takaya, J.; Tadami, S.; Ukai, K.; Iwasawa, N. Org. Lett. 2008, 10, 2697.
(c) Ukai, K.; Aoki, M.; Takaya, J.; Iwasawa. N. J. Am. Chem. Soc. 2006, 128, 8706.
(d) Zhang, X.; Zhang, W.-Z.; Shi, L.-L.; Guo, C.-X.; Zhang, L.-L.; Lu, X.-B. Chem. Commun. 2012, 48, 6292.
(e) Wang, W.-L; Zhang, G.-D.; Lang, R.; Xia, C.-G.; Li, F.-W. Green Chem. 2013, 15, 635.
[9] (a) Sasano, K.; Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2013, 135, 10954.
(b) Zhang, L.; Hou, Z.-M. Pure Appl. Chem. 2012, 84, 1705.
(c) Ackermann. L. Angew. Chem., Int. Ed. 2011, 50, 3842.
(d) Boogaerts, I. I. F.; Nolan, S. P. J. Am. Chem. Soc. 2010, 132, 8858.
(e) Boogaerts, I. I. F.; Fortman, G. C.; Furst, M. R. L.; Cazin, C. S. J.; Nolan, S. P. Angew. Chem., Int. Ed. 2010, 49, 8674.
(f) Zhang, L.; Cheng, J.; Ohishi, T.; Hou. Z. Angew. Chem. Int. Ed. 2010, 49, 8670.
(g) Inomata, H.; Ogata, K.; Fukuzawa, S. I.; Hou Z. Org. Lett. 2012, 14, 3986.
(h) Vechorkin, O.; Hirt, N.; Hu, X. Org. Lett. 2010, 12, 3567.
[10] Manjolinho, F.; Arndt, M.; Gooßen, K.; Gooßen, L. J. ACS Catal. 2012, 2, 2014.
[11] (a) Yu, B.; Diao, Z.-F.; Guo, C.-X.; Zhong, C.-L.; He, L.-N.; Zhao, Y.-N.; Song, Q.-W.; Liu, A.-H.; Wang, J.-Q. Green Chem. 2013, 15, 2401.
(b) Inamoto, K.; Asano, N.; Kobayashi, K.; Yonemoto, M.; Kondo, Y. Org. Biomol. Chem. 2012, 10, 1514.
(c) Zhang, W.-Z.; Li, W.-J.; Zhang, X.; Zhou, H.; Lu, X. B. Org. Lett. 2010, 12, 4748.
(d) Oi, S.; Fukue, Y.; Nemoto, K.; Inoue, Y. Macromolecules 1996, 29, 2694.
(e) Fukue, Y.; Oi, S.; Inoue, Y. J. Chem. Soc., Chem. Commun. 1994, 2091.
[12] Gooßen, L. J.; Rodrguez, N.; Manjolinho, F.; Lange, P. P. Adv. Synth. Catal. 2010, 352, 2913.
[13] Yu, D.; Zhang, Y. Proc. Natl. Acad. Sci. U. S. A.2010, 107, 20184.
[14] Yu, D.; Tan, M. X.; Zhang, Y. Adv. Synth. Catal. 2012, 354, 969.
[15] Yu, D.; Zhang, Y. Green Chem. 2011, 13, 1275.
[16] Ouyang, K.-B.; Xi, Z.-F. Acta Chim. Sinica 2013, 71, 13 (in Chinese).
(欧阳昆冰, 席振峰, 化学学报, 2013, 71, 13.)
[17] (a) Zhang, Y.-P.; Bian, M.; Yao, W.-J.; Gu, J.-M.; Ma, C. Chem. Commun. 2009, 4729.
(b) Qi, C.; Jiang, H.; Huang, L.; Yuan, G.; Ren, Y. Org. Lett. 2011, 13, 5520.
(c) Zheng, D.-Q.; Li, S.-Y.; Wu, J. Org. Lett. 2012, 14, 2655.
(d) Li, Z.-G.; Sun, H.-B.; Jiang, H.-L.; Liu, H. Org. Lett. 2008, 10, 3263.
[18] (a) Yoshida, M.; Komatsuzaki, Y.; Ihara, M. Org. Lett. 2008, 10, 2083.
(b) Heldebrant, D. J.; Yonker, C. R.; Jessop, P. G.; Phan, L. Energy Environ. Sci. 2008, 1, 487.
(c) Dinsmore, C. J.; Mercer, S. P. Org. Lett. 2004, 6, 2885.
[19] Yoshida, M.; Mizuguchi, T.; Shishido, K. Chem. Eur. J. 2012, 18, 15578.
[20] Li, J.-H.; Jia, L.-Q.; Jiang, H.-F. Chin. J. Org. Chem. 2000, 20, 293 (in Chinese).
(李金恒, 贾兰齐, 江焕峰, 有机化学, 2000, 20, 293.)
[21] Ma, L.; Dolphin, D. J. Chem. Soc., Chem. Commun. 1995, 2251.
[22] (a) Wang, Y.; Han, Q.-Z.; Wen, H. Mol. Simul. 2013, 39, 822.
(b) Heldebrant, D. J.; Jessop, P. G.; Thomas, C. A.; Eckert, C. A.; Liotta, C. L. J. Org. Chem. 2005, 70, 5335.
(c) Endo, T.; Nagai, D.; Monma, T.; Yamaguchi, H.; Ochiai, B. Macromolecules 2004, 37, 2007.
[23] Wang, X.; Lim, Y. N.; Lee, C.; Jang, H.-Y.; Lee, B. Y. Eur. J. Org. Chem. 2013, 1867.

超临界二氧化碳介质中端炔C—H键与CO₂的羧化反应研究

A Study on C—H Carboxylation Reaction of Terminal Alkynes with CO₂in Supercritical CO₂

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超临界二氧化碳介质中端炔C—H键与CO2的羧化反应研究