Citation: 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 shu

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

College of Science, Huazhong Agricultural University, Wuhan 430070

Corresponding author: Shi Wei, shiwei@mail.hzau.edu.cn
Received Date: 20 July 2016
Revised Date: 19 September 2016

Fund Project: the Natural Science Foundation of Hubei Province 2014CFB930the National Natural Science Foundation of China 21202050

Figures(2)

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.
- 1, 4-dioxane,
- deprotection,
- terminal alkyne,
- 2-methyl-3-butyn-2-ol
1. [1]
  Siemsen, P.; Livingston, R. C.; Diederich, F. Angew. Chem., Int. Ed. 2000, 39, 2632. doi: 10.1002/(ISSN)1521-3773
2. [2]
  Shun, A. L. K. S.; Tykwinski, R. R. Angew. Chem., Int. Ed. 2006, 45, 1034. doi: 10.1002/(ISSN)1521-3773
3. [3]
  Ross, C.; Scherlach, K.; Kloss, F.; Hertweck, C. Angew. Chem., Int. Ed. 2014, 53, 7794. doi: 10.1002/anie.201403344
4. [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. [5]
  Chalifoux, W. A.; Tykwinski, R. R. Nat. Chem. 2010, 2, 967. doi: 10.1038/nchem.828
6. [6]
  Shi, W. Curr. Organocatal. 2015, 2, 2. doi: 10.2174/2213337201666140820225700
7. [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. [8]
  Shi, W.; Lei, A. Tetrahedron Lett. 2014, 55, 2763. doi: 10.1016/j.tetlet.2014.03.022
9. [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. doi: 10.1002/chem.201301642
10. [10]
  Sahnoune, H.; Baranova, Z.; Bhuvanesh, N.; Gladysz, J. A.; Halet, J.-F. Organometallics 2013, 32, 6360. doi: 10.1021/om400709q
11. [11]
  Bai, D.; Li, C.; Li, J.; Jia, X. Chin. J. Org. Chem. 2012, 32, 994 (in Chinese). doi: 10.6023/cjoc1202073
12. [12]
  Wang, Y.-F.; Deng, W.; Liu, L.; Guo, Q.-X. Chin. J. Org. Chem. 2005, 25, 8 (in Chinese).
13. [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. doi: 10.1021/ja8049436
14. [14]
  Zhang, F.-G.; Ma, H.; Zheng, Y.; Ma, J.-A. Tetrahedron 2012, 68, 7663. doi: 10.1016/j.tet.2012.05.086
15. [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. doi: 10.1021/ja5004747
16. [16]
  Carpita A., Mannocci L., Rossi R.. Eur. J. Org. Chem.[J]. , 20051859.
17. [17]
  Li, S.; Mao, F.; Shi, Y.; Wang, Y.; Shi, W. J. Fujian Normal Univ. (Nat. Sci.) 2015, 31, 120 (in Chinese).
18. [18]
  Jiang, M. X.-W.; Rawat, M.; Wulff, W. D. J. Am. Chem. Soc. 2004, 126, 5970. doi: 10.1021/ja049836i
19. [19]
  Havens, S. J.; Hergenrother, P. M. J. Org. Chem. 1985, 50, 1763. doi: 10.1021/jo00210a042
20. [20]
  Danilkina, N. A.; Kulyashova, A. E.; Khlebnikov, A. F.; Bräse, S.; Balova, I. A. J. Org. Chem. 2014, 79, 9018. doi: 10.1021/jo501396s
21. [21]
  West, K.; Wang, C.; Batsanov, A. S.; Bryce, M. R. J. Org. Chem. 2006, 71, 8541. doi: 10.1021/jo0615697
22. [22]
  Li, J.; Huang, P. Beilstein J. Org. Chem. 2011, 7, 426. doi: 10.3762/bjoc.7.55
23. [23]
  Li, J.; Guo, K.; Dong, Q.; Huang, P.; Wang, H.; Xu, B. CN 104177209, 2014 [Chem. Abstr. 2014, 2020360].
24. [24]
  Kabalka, G. W.; Zhou, L.-L.; Wang, L.; Pagni, R. M. Tetrahedron 2006, 62, 857. doi: 10.1016/j.tet.2005.10.049
25. [25]
  Ghaffarzadeh, M.; Bolourtchian, M.; Fard, Z. H.; Halvagar, M. R.; Mohsenzadeh, F. Synth. Commun. 2006, 36, 1973. doi: 10.1080/00397910600634100
26. [26]
  Vaughn, T. H.; Nieuwland, J. A. J. Am. Chem. Soc. 1934, 56, 1207. doi: 10.1021/ja01320a065
1. [1]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
2. [2]
  Aiyi Xin , Jiawei Li , Xinyang Ran , Chuanjiang Fu , Zhiguo Wang . Collaborative Science and Education Based Experimental Design in Organic Chemistry: A Case Study of the Nucleophilic Substitution Reaction of 2-Hydroxymethyl-4,6-Di-Tert-Butylphenol. University Chemistry, 2025, 40(5): 366-375. doi: 10.12461/PKU.DXHX202407031
3. [3]
  Yuanyuan Ping , Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092
4. [4]
  Yuexiang Liu , Xiangqiao Yang , Tong Lin , Guantian Yang , Xiaoyong Xu , Bubing Zeng , Zhong Li , Weiping Zhu , Xuhong Qian . Efficient continuous synthesis of 2-[3-(trifluoromethyl)phenyl]malonic acid, a key intermediate of Triflumezopyrim, coupling with esterification-condensation-hydrolysis. Chinese Chemical Letters, 2025, 36(1): 109747-. doi: 10.1016/j.cclet.2024.109747
5. [5]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
6. [6]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
7. [7]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Corrosion inhibition of nickel-cobalt-phosphide in water by coating TiO₂ layer. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 365-384. doi: 10.11862/CJIC.20240063
8. [8]
  Yihui Song , Shangshang Qin , Kai Wu , Chengyun Jin , Bin Yu . 生物化学在高水平创新型药学人才培养中的交叉融合应用——以去甲基化酶LSD1抑制剂的活性评价为例. University Chemistry, 2025, 40(6): 341-352. doi: 10.12461/PKU.DXHX202406018
9. [9]
  Shuhui Li , Rongxiuyuan Huang , Yingming Pan . Electrochemical Synthesis of 2,5-Diphenyl-1,3,4-Oxadiazole: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 357-365. doi: 10.12461/PKU.DXHX202407028
10. [10]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
11. [11]
  Xiaoyang Li , Xiaowei Huang , Yimeng Zhang , Huan Liu , Shao Jin , Junpeng Zhuang . Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent. University Chemistry, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035
12. [12]
  Yue Li , Minghao Fan , Conghui Wang , Yanxun Li , Xiang Yu , Jun Ding , Lei Yan , Lele Qiu , Yongcai Zhang , Longlu Wang . 3D layer-by-layer amorphous MoS_x assembled from [Mo₃S₁₃]^2- clusters for efficient removal of tetracycline: Synergy of adsorption and photo-assisted PMS activation. Chinese Chemical Letters, 2024, 35(9): 109764-. doi: 10.1016/j.cclet.2024.109764
13. [13]
  Anqiu LIU , Long LIN , Dezhi ZHANG , Junyu LEI , Kefeng WANG , Wei ZHANG , Junpeng ZHUANG , Haijun HAO . Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424
14. [14]
  Kangmin Wang , Liqiu Wan , Jingyu Wang , Chunlin Zhou , Ke Yang , Liang Zhou , Bijin Li . Multifunctional 2-(2′-hydroxyphenyl)benzoxazoles: Ready synthesis, mechanochromism, fluorescence imaging, and OLEDs. Chinese Chemical Letters, 2024, 35(10): 109554-. doi: 10.1016/j.cclet.2024.109554
15. [15]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
16. [16]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
17. [17]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
18. [18]
  Guoze Yan , Bin Zuo , Shaoqing Liu , Tao Wang , Ruoyu Wang , Jinyang Bao , Zhongzhou Zhao , Feifei Chu , Zhengtong Li , Yusuke Yamauchi , Saad Melhi , Xingtao Xu . Opportunities and Challenges of Capacitive Deionization for Uranium Extraction from Seawater. Acta Physico-Chimica Sinica, 2025, 41(4): 100032-. doi: 10.3866/PKU.WHXB202404006
19. [19]
  Gaofeng WANG , Shuwen SUN , Yanfei ZHAO , Lixin MENG , Bohui WEI . Structural diversity and luminescence properties of three zinc coordination polymers based on bis(4-(1H-imidazol-1-yl)phenyl)methanone. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 849-856. doi: 10.11862/CJIC.20230479
20. [20]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027

Get Citation

PDF

XML

Metrics

PDF Downloads(36)
Abstract views(2887)
HTML views(601)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142