Chinese Journal of Organic Chemistry >
Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions
Received date: 2016-07-20
Revised date: 2016-09-19
Online published: 2016-10-11
Supported by
Project supported by the National Natural Science Foundation of China (No. 21202050), and the Natural Science Foundation of Hubei Province (No. 2014CFB930).
Terminal alkynes are important building blocks in organic synthesis. Acetone protected terminal alkynes are frequently used in alkyne synthesis and reactions, which could be easily prepared by Pd-catalyzed Sonogashira cross-coupling reactions between electrophiles and 2-methyl-3-butyn-2-ol. At present, the deprotection of the acetone protected terminal alkynes is generally carried out in reflux toluene in the presence of potassium hydroxide for hours. However, this procedure suffers from the harsh reaction conditions and its application has been limited. Here in the deprotection of acetones has been discussed, and various solvent, temperature, substrates were investigated to advance the procedure, and it is found that by employing 1,4-dioxane as solvent, this process can undergo smoothly at 60℃ with satisfying yields in 0.5~2 h in the presence of 2.0 equiv. KOH.
Key words： 1,4-dioxane; deprotection; terminal alkyne; 2-methyl-3-butyn-2-ol
Guan Zhipeng , Shi Yao , Shi Wei , Chen Hao . Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions[J]. Chinese Journal of Organic Chemistry, 2017 , 37(2) : 418 -422 . DOI: 10.6023/cjoc201607032
[1] Siemsen, P.; Livingston, R. C.; Diederich, F. Angew. Chem., Int. Ed. 2000, 39, 2632.
[2] Shun, A. L. K. S.; Tykwinski, R. R. Angew. Chem., Int. Ed. 2006, 45, 1034.
[3] Ross, C.; Scherlach, K.; Kloss, F.; Hertweck, C. Angew. Chem., Int. Ed. 2014, 53, 7794.
[4] Tykwinski, R. R.; Chalifoux, W.; Eisler, S.; Lucotti, A.; Tommasini, M.; Fazzi, D.; Del, Z. M.; Zerbi, G. Pure Appl. Chem. 2010, 82, 891.
[5] Chalifoux, W. A.; Tykwinski, R. R. Nat. Chem. 2010, 2, 967.
[6] Shi, W. Curr. Organocatal. 2015, 2, 2.
[7] Tykwinski, R. R.; Chalifoux, W.; Eisler, S.; Lucotti, A.; Tommasini, M.; Fazzi, D.; Del Zoppo, M.; Zerbi, G. Pure Appl. Chem. 2010, 82, 891.
[8] Shi, W.; Lei, A. Tetrahedron Lett. 2014, 55, 2763.
[9] Stefko, M.; Tzirakis, M. D.; Breiten, B.; Ebert, M.-O.; Dumele, O.; Schweizer, W. B.; Gisselbrecht, J.-P.; Boudon, C.; Beels, M. T.; Biaggio, I.; Diederich, F. Chem.-Eur. J. 2013, 19, 12693.
[10] Sahnoune, H.; Baranova, Z.; Bhuvanesh, N.; Gladysz, J. A.; Halet, J.-F. Organometallics 2013, 32, 6360.
[11] Bai, D.; Li, C.; Li, J.; Jia, X. Chin. J. Org. Chem. 2012, 32, 994 (in Chinese).(白东虎, 李春举, 李健, 贾学顺, 有机化学, 2012, 32, 994.)
[12] Wang, Y.-F.; Deng, W.; Liu, L.; Guo, Q.-X. Chin. J. Org. Chem. 2005, 25, 8 (in Chinese).(王晔峰, 邓维, 刘磊, 郭庆祥, 有机化学, 2005, 25, 8.)
[13] Shi, W.; Luo, Y. D.; Luo, X. C.; Chao, L.; Zhang, H.; Wang, J.; Lei, A. W. J. Am. Chem. Soc. 2008, 130, 14713.
[14] Zhang, F.-G.; Ma, H.; Zheng, Y.; Ma, J.-A. Tetrahedron 2012, 68, 7663.
[15] Xue, Y.-X.; Zhu, Y.-Y.; Gao, L.-M.; He, X.-Y.; Liu, N.; Zhang, W.-Y.; Yin, J.; Ding, Y.; Zhou, H.; Wu, Z.-Q. J. Am. Chem. Soc. 2014, 136, 4706.
[16] Carpita, A.; Mannocci, L.; Rossi, R. Eur. J. Org. Chem. 2005, 1859.
[17] Li, S.; Mao, F.; Shi, Y.; Wang, Y.; Shi, W. J. Fujian Normal Univ. (Nat. Sci.) 2015, 31, 120 (in Chinese).(李硕, 毛凤, 师瑶, 王阳, 石炜, 福建师范大学学报(自然科学版), 2015, 31, 120.)
[18] Jiang, M. X.-W.; Rawat, M.; Wulff, W. D. J. Am. Chem. Soc. 2004, 126, 5970.
[19] Havens, S. J.; Hergenrother, P. M. J. Org. Chem. 1985, 50, 1763.
[20] Danilkina, N. A.; Kulyashova, A. E.; Khlebnikov, A. F.; Bräse, S.; Balova, I. A. J. Org. Chem. 2014, 79, 9018.
[21] West, K.; Wang, C.; Batsanov, A. S.; Bryce, M. R. J. Org. Chem. 2006, 71, 8541.
[22] Li, J.; Huang, P. Beilstein J. Org. Chem. 2011, 7, 426.
[23] Li, J.; Guo, K.; Dong, Q.; Huang, P.; Wang, H.; Xu, B. CN 104177209, 2014 [Chem. Abstr. 2014, 2020360].
[24] Kabalka, G. W.; Zhou, L.-L.; Wang, L.; Pagni, R. M. Tetrahedron 2006, 62, 857.
[25] Ghaffarzadeh, M.; Bolourtchian, M.; Fard, Z. H.; Halvagar, M. R.; Mohsenzadeh, F. Synth. Commun. 2006, 36, 1973.
[26] Vaughn, T. H.; Nieuwland, J. A. J. Am. Chem. Soc. 1934, 56, 1207.
/
| 〈 |
|
〉 |
