Citation: 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. doi: 10.6023/cjoc202005094 shu

Recent Progress of Protecting Groups for Terminal Alkynes

Hu Zhifang ^a ,
Peng Lifen ^a,b,, ,
Qiu Renhua ^b,, ,
Orita Akihiro ^c,,

a.
Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201, China
b.
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
c.
Department of Chemistry, Okayama University of Science, Okayama 700-0005, Japan

Corresponding author: Peng Lifen, 1060137@hnust.edu.cn Qiu Renhua, renhuaqiu1@hnu.edu.cn Orita Akihiro, orita@dac.ous.ac.jp
Received Date: 31 May 2020
Revised Date: 2 July 2020
Available Online: 22 July 2020
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21802040), the Natural Science Fund Youth Project of Hunan Province (No. 2018JJ3145) and the Open Foundation of Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology (No. E21843)the National Natural Science Foundation of China 21802040the Open Foundation of Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology E21843the Natural Science Fund Youth Project of Hunan Province 2018JJ3145

Figures(14)

The protection/deprotection of functional group is one of the fundamental technologies in organic synthesis. An ideal protecting group needs to satisfy the following issues:facile introduction, stability and facile deprotection. Protection of an acetylenic hydrogen is often necessary because of its acidity. In this review, the recent progress of protecting groups for terminal alkyne is highlighted. Based on different polarity of protecting groups, less polar protecting groups such as trimethylsilyl (TMS), trimethylgermanium group (Me₃Ge) and high polar protecting groups like (3-cyanopropyl)dimethylsilyl (CPDMS), (3-cyanopropyl)diisopropylsilyl (CPDIPS) and diphenylphosphoryl (Ph₂P(O)) are introduced in detail.
- protecting group,
- terminal alkyne,
- Sonogashira coupling
1. [1]
  Greene, T. W.; Wuts. P. G. M. Protective Groups in Organic Synthesis, 3th ed., John Wiley & Sons, Inc., New York, 1999.
2. [2]
  (a) Stang, P. J.; Diederich. F. Modern Acetylene Chemistry, VCH, Weinheim, 1995.
  (b) Diederich, F.; Stang, P. J.; Tykwinski, R. R. Acetylene Chemistry, Willey-VCH Verlag GmbH & CO. KgaA, Weinheim, 2005.
  (c) Peng, L.-F.; Zhang, S.-W.; Wang, B.-H.; Xun, M.-S.; Tang, Z.-L.; Jiao, Y.-C.; Xu, X.-H. Chin. J. Org. Chem. 2018, 38, 519(in Chinese).
  (彭丽芬, 张思维, 王丙昊, 寻梦硕, 唐子龙, 焦银春, 许新华, 有机化学, 2018, 38, 519.)
  (d) Peng, L.-F.; Wang, B.-H.; Wang, M.; Tang, Z.-L.; Jiang, Y.-Z.; Jiao, Y.-C.; Xu, X.-H. J. Chem. Res. 2018, 42, 235.
  (e) Wang, Z.; Yang, L.; Liu, H.-L.; Bao, W.-H.; Tan, Y.-Z.; Wang, M.; Tang, Z.; He, W.-M. Chin. J. Org. Chem. 2018, 38, 2639(in Chinese).
  (王峥, 杨柳, 刘慧兰, 谭英芝, 包文虎, 汪明, 唐子龙, 何卫民, 有机化学, 2018, 38, 2639.)
  (f) Peng, L.-F.; Lei, J.-Y.; Wu, L.; Tang, Z.-L.; Luo, Z.-P.; Jiao, Y.-C.; Xu, X.-H. J. Chem. Res. 2018, 42, 271.
  (g) Li, W.-Y.; Yin, G.-X.; Huang, L.; Xiao, Y.; Fu, Z.-M.; Xin, X.; Liu, F.; Li, Z.-Z. He, W.-M. Green Chem. 2016, 18, 4879.
  (h) Wu, C.; Wang, Z.; Hu, Z.; Zeng, F.; Zhang, X.-Y.; Cao, Z.; Tang, Z.; . He, W.-M.; Xu, X.-H. Org. Biomol. Chem. 2018, 16, 3177.
  (i) Peng, L.-F.; Peng, C.; Wang, M.; Tang, Z.-L.; Jiao, Y.-C.; Xu, X.-H. Chin. J. Org. Chem. 2018, 38, 3048(in Chinese).
  (彭丽芬, 彭超, 汪明, 唐子龙, 焦银春, 许新华, 有机化学, 2018, 38, 3048.)
  (j) Wu, L.; Peng, L.-F.; Hu, Z.-F.; Wang, H.; Tang, Z.-L.; Jiao Y.-C.; Xu, X.-H. J. Chem. Res. 2019, 43, 503.
3. [3]
  (a) Mao, G.; Orita, A.; Fenenko, L.; Yahiro, M.; Adachi, C.; Otera, J. Mater. Chem. Phys. 2009, 115, 378.
  (b) Fenenko, L.; Shao, G.; Orita, A.; Yahiro, M.; Otera, J.; Svechnikov, S.; Adachi, C. Chem. Commun. 2007, 2278.
  (c) Matsuo, D.; Yang, X.; Hamada, A.; Morimoto, K.; Kato, T.; Yahiro, M.; Adachi, C.; Orita, A.; Otera, J. Chem. Lett. 2010, 39, 1300.
  (d) Oyamada, T.; Shao, G.; Uchiuzou, H.; Nakanotani, H.; Orita, A.; Otera, J.; Yahiro, M.; Adachi, C. Jpn. J. Appl. Phys., Part 2 2006, 45, 46.
  (e) Yang, X.; Kajiyama, S.; Fang, J.-K.; Xu, F.; Uemura, Y.; Koumura, N.; Hara, K.; Orita, A.; Otera, J. Bull. Chem. Soc. Jpn. 2012, 85, 687.
  (f) Yang, X.; Fang, J.-K.; Suzuma, Y.; Xu, F.; Orita, A.; Otera, J.; Kajiyama, S.; Koumura, N.; Hara, K. Chem. Lett. 2011, 40, 620.
  (g) Peng, L.-F.; Hu, Z.-F.; Wang, H.; Wu, L.; Jiao, Y.-C.; Tang, Z.-L.; Xu, X.-H. RSC. Adv. 2020, 10232.
  (h) Peng, L.-F.; Lei, J.-Y.; Wu, L.; Tang, Z.-L.; Luo, Z.-P.; Jiao Y.-C.; Xu, X.-H. J. Chem. Res. 2018, 42, 271.
  (i) Peng, L.-F.; Li, R.-Z.; Tang, Z.-L.; Chen, J.-Y.; Yi, R.-N.; Xu, X.-H. Tetrahedron 2017, 73, 3099.
  (l) Peng, L.-F.; Jiang, J.; Peng, C.; Dai, N.-N.; Tang, Z.-L.; Jiao Y.-C.; Chen, J.-Y.; Xu, X.-H. Chin. J. Org. Chem. 2017, 37, 3013(in Chinese).
  (彭丽芬, 蒋娟, 彭超, 代宁宁, 唐子龙, 焦银春, 陈锦杨, 许新华, 有机化学, 2017, 37, 3013.)
  (m) Peng, L.-F.; Hu, Z.-F.; Lu, Q.-C.; Tang, Z.-L.; Jiao Y.-C.; Xu, X.-H. Chin. Chem. Lett. 2019, 30, 2151.
  (n) Wu, L.; Peng, L.-F.; Hu, Z.-F.; Jiao, Y.-C.; Tang, Z.-L.; Xu, X.-H. Curr. Org. Synth. 2020, 17, 271.
4. [4]
  (a) Rankin, G. M.; Maxwell-Cameron, I.; Painter, G. F.; Larsen, D. S. J. Org. Chem. 2013, 78, 5264.
  (b) Urones, B.; Gómez Arrayás, R.; Carretero, J. C. Org. Lett. 2013, 15, 1120.
  (c) Balbuena, P.; Gonçalves-Pereira, R.; Jiménez Blanco, J. L.; García-Moreno, M. I.; Lesur, D.; Ortiz Mellet, C.; García Fernández, J. M. J. Org. Chem. 2013, 78, 1390.
  (d) Muranaka, K.; Ichikawa, S.; Matsuda, A. J. Org. Chem. 2011, 76, 9278.
  (e) Ihara, H.; Koyanagi, M.; Suginome, M. Org. Lett. 2011, 13, 2662.
  (f) Liang, H.; Corey, E. J. Org. Lett. 2011, 13, 4120.
5. [5]
  (a) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 2857.
  (b) Andreev, A. A.; Konshin, V. V.; Komarov, N. V.; Rubin, M.; Brouwer, C.; Gevorgyan, V. Org. Lett. 2004, 6, 421.
  (c) Jiang, H.; Zhu, S. Tetrahedron Lett. 2005, 46, 517.
6. [6]
  Ernst, A.; Gobbi, L.; Vasella, A. Tetrahedron Lett. 1996, 37, 7959. doi: 10.1016/0040-4039(96)01838-2
7. [7]
  Höger, S.; Bonrad, K. J. Org. Chem. 2000, 65, 2243. doi: 10.1021/jo991746m
8. [8]
  Gaefke, G.; Höger, S. Synthesis 2008, 2155.
9. [9]
  Yang, X.; Matsuo, D.; Suzuma, Y.; Fang, J.-K.; Xu, F.; Orita, A.; Otera, J. Synlett 2011, 2402.
10. [10]
  (a) Ito, H.; Arimoto, K.; Senusui, H.O.; Hosomi, A. Tetrahedron Lett. 1997, 38, 3977.
  (b) Sugita, H.; Hatanaka, Y.; Hiyama, T. Chem. Lett. 1996, 25, 379.
11. [11]
  Davidsohn, W. E.; Henry, M. C. Chem. Rev. 1967, 67, 73. doi: 10.1021/cr60245a003
12. [12]
  (a) Cai, C.; Vasella, A. Helv. Chim. Acta 1995, 78, 732.
  (b) Nishikawa, T.; Ino, A.; Isobe, M.; Tetrahedron 1994, 50, 1449.
  (c) Scott, L. T.; Cooney, M. J.; Johnels, D. J. Am. Chem. Soc. 1990, 112, 4054.
  (d) Lu, Y.-F.; Fallis, A. G. Tetrahedron Lett. 1993, 34, 3367.
  (e) Nielsen, M. B.; Diederich, F. Synlett 2002, 544.
  (f) Tobe, Y.; Utsumi, N.; Kawabata, K.; Naemura, K. Tetrahedron Lett. 1996, 37, 9325.
13. [13]
  Nishikawa, T.; Ino, A.; Isobe, M. Tetrahedron 1994, 50, 1449. doi: 10.1016/S0040-4020(01)80629-3
14. [14]
  Chinchilla, R.; Nájera, C. Chem. Rev. 2007, 107, 874. doi: 10.1021/cr050992x
15. [15]
  Li, H.-B.; Petersen, J. L.; Wang, K.-K. J. Org. Chem. 2001, 66, 7804. doi: 10.1021/jo010687l
16. [16]
  (a) Haley, M. M.; Bell, M. L.; English, J. J.; Johnson, C. A.; Weakley, T. J. R. J. Am. Chem. Soc. 1997, 119, 2956.
  (b) Bell, M. L.; Chiechi, R. C.; Johnson, C. A.; Kimbal, D. B.; Matzger, A.; Wan, W. B.; Weakley, T. J. R.; Haley, M. M. Tetrahedron 2001, 57, 3507.
17. [17]
  (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467.
  (b) Tohda, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1977, 777.
  (c) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627.
18. [18]
  Peng, L.-F.; Xu, F.; Suzuma, Y.; Orita, A.; Otera, J. J. Org. Chem. 2013, 78, 12802. doi: 10.1021/jo402176w
19. [19]
  Peng, L.-F.; Xu, F.; Shinohara, K.; Orita, A.; Otera, J. Chem. Lett. 2014, 43, 1610. doi: 10.1246/cl.140579
20. [20]
  Tahara, K.; Furukawa, S.; Uji-i, H.; Uchino, T.; Ichikawa, T.; Zhang, J.; Mandouh, W.; Sonoda, M.; Schryver, F. C. D.; Feyter, S. D.; Tobe, Y. J. Am. Chem. Soc. 2006, 128, 16613. doi: 10.1021/ja0655441
21. [21]
  (a) Peña-López, M.; Ayán-Varela, M.; Sarandeses, L. A.; Sestelo, J. P. Chem. Eur. J. 2010, 16, 9905.
  (b) Dogan, J.; Schulte, J. B.; Swiegers, G. F.; Wild, S. B. J. Org. Chem. 2000, 65, 951.
  (c) Lu, E.; Chen, Y.; Zhou, J.; Leng, X. Organometallics 2012, 31, 4574.
22. [22]
  (a) Kosugi, M.; Fugami, K. Handbook of Organopalladium Chemistry for Organic Synthesis, Ed.: Negishi, E., Wiley, New York, 2002.
  (b) Tsuji, J. Palladium Reagents and Catalysts, Wiley, Chichester, U. K. 2004.
  (c) Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
23. [23]
  Warner, B. P.; Buchwald, S. L. J. Org. Chem. 1994, 59, 5822. doi: 10.1021/jo00098a052
24. [24]
  (a) Mössinger, D.; Jester, S. S.; Sigmund, E.; Müller, U.; Höger, S. Macromolecules 2009, 42, 7974.
  (b) Nicolaou, K. C.; Zipkin, R. E.; Petasis, N. A. J. Am. Chem. Soc. 1982, 104, 5558.
25. [25]
  Peña-López, M.; Ayán-Varela, M.; Sarandeses, L. A.; Sestelo, J. P. Chem. Eur. J. 2010, 16, 9905. doi: 10.1002/chem.201000726
26. [26]
  (a) Peng, L.-F.; Xu, F.; Shinohara, K.; Orita, A.; Otera, J. Org. Chem. Front. 2015, 2, 248.
  (b) Ikegashira, K.; Nishihara, Y.; Hirabayashi, K.; Mori, A.; Hiyama, T. Chem. Commun. 1997, 1039.
  (c) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Chem. Lett. 1997, 26, 1233.
  (d) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780.
1. [1]
  Mei Peng , Wei-Min He . Photochemical synthesis and group transfer reactions of azoxy compounds. Chinese Chemical Letters, 2024, 35(8): 109899-. doi: 10.1016/j.cclet.2024.109899
2. [2]
  Hang Chen , Chengzhi Cui , Hebo Ye , Hanxun Zou , Lei You . Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups. Chinese Chemical Letters, 2024, 35(5): 109145-. doi: 10.1016/j.cclet.2023.109145
3. [3]
  Zhili Li , Qijun Wo , Dongdong Huang , Dezhong Zhou , Lei Guo , Yeqing Mao . Improving gene transfection efficiency of highly branched poly(β-amino ester)s through the in-situ conversion of inactive terminal groups. Chinese Chemical Letters, 2024, 35(8): 109737-. doi: 10.1016/j.cclet.2024.109737
4. [4]
  Jian-Rong Li , Jieying Hu , Lai-Hon Chung , Jilong Zhou , Parijat Borah , Zhiqing Lin , Yuan-Hui Zhong , Hua-Qun Zhou , Xianghua Yang , Zhengtao Xu , Jun He . Insight into stable, concentrated radicals from sulfur-functionalized alkyne-rich crystalline frameworks and application in solar-to-vapor conversion. Chinese Journal of Structural Chemistry, 2024, 43(8): 100380-100380. doi: 10.1016/j.cjsc.2024.100380
5. [5]
  Qijun Tang , Wenguang Tu , Yong Zhou , Zhigang Zou . High efficiency and selectivity catalyst for photocatalytic oxidative coupling of methane. Chinese Journal of Structural Chemistry, 2023, 42(12): 100170-100170. doi: 10.1016/j.cjsc.2023.100170
6. [6]
  Kongchuan Wu , Dandan Lu , Jianbin Lin , Ting-Bin Wen , Wei Hao , Kai Tan , Hui-Jun Zhang . Elucidating ligand effects in rhodium(Ⅲ)-catalyzed arene–alkene coupling reactions. Chinese Chemical Letters, 2024, 35(5): 108906-. doi: 10.1016/j.cclet.2023.108906
7. [7]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147
8. [8]
  Xin Huang , Yi Zhao , Wanzhen Liang . Vibronic coupling effect on intersystem crossing rates of TADF emitters. Chinese Journal of Structural Chemistry, 2024, 43(6): 100278-100278. doi: 10.1016/j.cjsc.2024.100278
9. [9]
  Jian Ji , Jie Yan , Honggen Peng . Modulation of dinuclear site by orbital coupling to boost catalytic performance. Chinese Journal of Structural Chemistry, 2024, 43(8): 100360-100360. doi: 10.1016/j.cjsc.2024.100360
10. [10]
  Wenhao Yan , Shuaiya Xue , Xuerui Zhao , Wei Zhang , Jian Li . Hexagonal boron nitride based slippery liquid infused porous surface with anti-corrosion, anti-contaminant and anti-icing properties for protecting magnesium alloy. Chinese Chemical Letters, 2024, 35(4): 109224-. doi: 10.1016/j.cclet.2023.109224
11. [11]
  Yuqing Wang , Zhemin Li , Qingjun Lu , Qizhao Li , Jiaxin Luo , Chengjie Li , Yongshu Xie . Solar cells based on doubly concerted companion dyes with the efficiencies modulated by inserting an ethynyl group at different positions. Chinese Chemical Letters, 2024, 35(5): 109093-. doi: 10.1016/j.cclet.2023.109093
12. [12]
  Run-Han Li , Tian-Yi Dang , Wei Guan , Jiang Liu , Ya-Qian Lan , Zhong-Min Su . Evolution exploration and structure prediction of Keggin-type group IVB metal-oxo clusters. Chinese Chemical Letters, 2024, 35(5): 108805-. doi: 10.1016/j.cclet.2023.108805
13. [13]
  Junchen Peng , Xue Yin , Dandan Dong , Zhongyuan Guo , Qinqin Wang , Minmin Liu , Fei He , Bin Dai , Chaofeng Huang . Promotion effect of epoxy group neighboring single-atom Cu site on acetylene hydrochlorination. Chinese Chemical Letters, 2024, 35(6): 109508-. doi: 10.1016/j.cclet.2024.109508
14. [14]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
15. [15]
  Wenyu Gao , Liming Zhang , Chuang Zhao , Lixiang Liu , Xingran Yang , Jinbo Zhao . Controlled semi-Pinacol rearrangement on a strained ring: Efficient access to multi-substituted cyclopropanes by group migration strategy. Chinese Chemical Letters, 2024, 35(9): 109447-. doi: 10.1016/j.cclet.2023.109447
16. [16]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
17. [17]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
18. [18]
  Lang Gao , Cen Zhou , Rui Wang , Feng Lan , Bohang An , Xiaozhou Huang , Xiao Zhang . Unveiling inverse vulcanized polymers as metal-free, visible-light-driven photocatalysts for cross-coupling reactions. Chinese Chemical Letters, 2024, 35(4): 108832-. doi: 10.1016/j.cclet.2023.108832
19. [19]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305
20. [20]
  Jun Guo , Zhenbang Zhuang , Wanqiang Liu , Gang Huang . "Co-coordination force" assisted rigid-flexible coupling crystalline polymer for high-performance aqueous zinc-organic batteries. Chinese Chemical Letters, 2024, 35(9): 109803-. doi: 10.1016/j.cclet.2024.109803

Get Citation

PDF

XML

Metrics

PDF Downloads(369)
Abstract views(4650)
HTML views(791)

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