Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions

doi:10.6023/cjoc201607032

Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (2): 418-422.DOI: 10.6023/cjoc201607032 Previous Articles Next Articles

ARTICLE

温和条件下去丙酮保护制备末端单炔烃及末端二炔的方法

关志朋, 师瑶, 石炜, 陈浩

华中农业大学理学院武汉 430070

收稿日期:2016-07-20 修回日期:2016-09-19 发布日期:2016-10-11
通讯作者: 石炜 E-mail:shiwei@mail.hzau.edu.cn
基金资助:
国家自然科学基金（No.21202050）、湖北省自然科学基金（No.2014CFB930）资助项目.

Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions

Guan Zhipeng, Shi Yao, Shi Wei, Chen Hao

College of Science, Huazhong Agricultural University, Wuhan 430070

Received:2016-07-20 Revised:2016-09-19 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).

1. Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions.PDF(560KB)

Abstract

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

Cite this article

Guan Zhipeng, Shi Yao, Shi Wei, Chen Hao. Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions[J]. Chin. J. Org. Chem., 2017, 37(2): 418-422.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[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.

温和条件下去丙酮保护制备末端单炔烃及末端二炔的方法

Synthesis of Terminal Alkynes/Diynes through Deprotection of Acetone Protected Alkynes under Mild Conditions

PDF

Supporting Info.

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Fei Chen, Sheng Tao, Ning Liu, Bin Dai. CNN-Type Binuclear Cu(I) Complexes Catalyzed Direct Carboxylation via the Fixation of CO₂ at Room Temperature [J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2471-2480.
[2]	Liwen Ma, Xiaoye Wei, Zilin Zhao, Ang Zhao, Xiangwen Deng, Bingnan Huo, Gang Ma, Chunfang Zhang. Theoretical Study on the Catalytic Mechanism of Copper with Various Valence for the Terminal Alkyne Coupling Reaction [J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1811-1819.
[3]	Yinyin Wang, Xiaowan Lin, Piao Zhang, Meihua Shen, Huadong Xu, Defeng Xu. Design and Synthesis of Pyridine and 1,3,5-Triazine PNP Pincer Ligands and Their Application in Cobalt Catalyzed Semihydrogenation of Terminal Alkynes [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3312-3320.
[4]	Jingru Liang, Bingying Wang, Chengyin Huang, Xiaojun Ye, Yanmei Wen. Synthesis of Symmetrical (E,E)-1,4-Diaryl-1,3-butadienes by One-Pot Method [J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 2116-2120.
[5]	Peng Zhou, Shangwei Feng, Huihua Qiu, Jiantao Zhang. Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes [J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 394-399.
[6]	Yao Ming, Zhang Jingjing, Yang Sen, Xiong Hangxing. γ-Aluminum Oxide-Mediated Iodination of Terminal Alkynes [J]. Chinese Journal of Organic Chemistry, 2020, 40(7): 2153-2158.
[7]	Hu Zhifang, Peng Lifen, Qiu Renhua, Orita Akihiro. Recent Progress of Protecting Groups for Terminal Alkynes [J]. Chinese Journal of Organic Chemistry, 2020, 40(10): 3112-3119.
[8]	Liu Zhuyun, Xu Juanjuan, Ling Bin, Li Yanxiang, Liu Guangcong, Wang Lizhong, Zhou Guochun. Synthesis of Benzyl Phenol from Benzyl Aryl Ether by Polyphosphoric Acid-Catalyzed Benzyl Rearrangement [J]. Chin. J. Org. Chem., 2019, 39(9): 2515-2524.
[9]	Wang, Yaqi, Yin, Qiang, Guo, Dun, Han, Limin, Sun, Qi, Hong, Hailong, Suo, Quanling, Suo. Quanling. Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide [J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2898-2905.
[10]	Zeng Yijie, Duan Yue, Zhao Hui, Hu Xiangguo. Efficient and Chemoselective Deprotection of N-t-Butyloxycarbonyl Group Mediated by Selectfluor [J]. Chin. J. Org. Chem., 2018, 38(7): 1712-1717.
[11]	Ma Nan, Zeng Xianghua. Cu₂O-Catalyzed Green Oxidative Terminal Alkynes Homocoupling without Bases [J]. Chin. J. Org. Chem., 2018, 38(6): 1556-1561.
[12]	Qi Haitang, Song Guanglin, Quan Zhengjun, Wang Xicun. CuSO₄·5H₂O/NaAsc-Catalyzed Sonogashira Coupling Reaction of Aryl Iodides and Terminal Alkynes [J]. Chin. J. Org. Chem., 2017, 37(7): 1855-1859.
[13]	Wang Chao, Deng Nan, Wang Lingling, Xu Dingjian, Yao Xiaoquan. Cu-Ag Bimetallic Nanoparticles Catalyzed Addition of Terminal Alkynes to Aldehydes [J]. Chin. J. Org. Chem., 2016, 36(5): 1034-1043.
[14]	Li Fuwei, Wang Xiaolong, Yu Haitao. Preparation of 1,3,5-Trisubstituted Pyrazoles with Cascade Reaction Catalyzed by Cu between Hydrazonoyl Halide and Terminal Alkynes [J]. Chin. J. Org. Chem., 2016, 36(5): 1127-1132.
[15]	Li Yibiao, Cheng Liang, Chen Lu, Li Bin, Sun Ning, Qing Ning. One-Pot Synthesis of Substituted Thiophene and Furan Derivatives from Terminal Alkynes [J]. Chin. J. Org. Chem., 2016, 36(10): 2426-2436.