Citation: Zeng Yijie, Duan Yue, Zhao Hui, Hu Xiangguo. Efficient and Chemoselective Deprotection of N-t-Butyloxycarbonyl Group Mediated by Selectfluor[J]. Chinese Journal of Organic Chemistry, ;2018, 38(7): 1712-1717. doi: 10.6023/cjoc201801036 shu

Efficient and Chemoselective Deprotection of N-t-Butyloxycarbonyl Group Mediated by Selectfluor

Zeng Yijie ^a ,
Duan Yue ^a ,
Zhao Hui ^b,, ,
Hu Xiangguo ^a,,

a.
National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022
b.
Anhui Engineering Technology Research Center for Extraction and Isolation of Active Components, Anhui Academy of Applied Technology, Hefei 230031

Corresponding author: Zhao Hui, zh1986@iccas.ac.cn Hu Xiangguo, huxiangg@iccas.ac.cn
Received Date: 25 January 2018
Revised Date: 12 February 2018
Available Online: 16 July 2018
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21502076), the Natural Science Foundation of Jiangxi Province (No. 20161BAB213068), the Hundred-Talent Program (Hefei) and the Outstanding Young Talent Program of Jiangxi Province (No. 20171BCB23039)the Hundred-Talent Program (Hefei) and the Outstanding Young Talent Program of Jiangxi Province 20171BCB23039the National Natural Science Foundation of China 21502076the Natural Science Foundation of Jiangxi Province 20161BAB213068

Figures(1)

Selectfluor, 1-chloromethyl-4-fluoro-1, 4-diazoniabicyclo-[2.2.2] octane bis(tetrafluoroborate), is among the most popular fluorinating reagents owning to its commercially availability and non-hygroscopic property. The discovery and understanding of new reactivities of selectfluor are thus important for reaction design and optimization when this popular reagent is employed. It has been found that selectfluor could selectively remove Boc group from doubly protected amines in acetonitrile. This deprotection could be of interest when compared to other reported methods, not only because selectfluor is a solid and easy-to-handle, but also because the reaction is mild, operationally simple and chemoselective. The potential usefulness of this method is demonstrated by the deprotection of a series of protected amino acids and a one-step synthesis of pharmaceutically important purine derivative. The NMR experiments conducted in CD₃CN explain why stoichiometric amount of selectfluor is needed for a successful reaction.
- selectfluor,
- t-butyloxycarbonyl,
- deprotection,
- selectivity,
- synthesis
1. [1]
  (a) Banks, R. E. ; Mohialdinkhaffaf, S. N. ; Lal, G. S. ; Sharif, I. ; Syvret, R. G. J. Chem. Soc., Chem. Commun. 1992, 595.
  (b) Nyffeler, P. T. ; Duron, S. G. ; Burkart, M. D. ; Vincent, S. P. ; Wong, C. H. Angew. Chem., Int. Ed. 2005, 44, 192.
2. [2]
  (a) Rueda-Becerril, M. ; Sazepin, C. C. ; Leung, J. C. T. ; Okbinoglu, T. ; Kennepohl, P. ; Paquin, J. F. ; Sammis, G. M. J. Am. Chem. Soc. 2012, 134, 4026.
  (b) Yin, F. ; Wang, Z. T. ; Li, Z. D. ; Li, C. Z. J. Am. Chem. Soc. 2012, 134, 10401.
  (c) Yan, H. ; Zhu, C. Sci. China: Chem. 2017, 60, 214.
3. [3]
  Stavber, S. Molecules 2011, 16, 6432. doi: 10.3390/molecules16086432
4. [4]
  Greene, T. W. ; Wuts, P. G. M. in Protective Groups in Organic Synthesis, Wiley, New York, 1999, pp. 518~525.
5. [5]
  Deniau, G.; Slawin, A. M. Z.; Lebl, T.; Chorki, F.; Issberner, J. P.; van Mourik, T.; Heygate, J. M.; Lambert, J. J.; Etherington, L. A.; Sillar, K. T.; O'Hagan, D. Chem. Biochem. 2007, 8, 2265.
6. [6]
  (a) Yadav, J. S. ; Subba Reddy, B. V. ; Reddy, K. S. Synlett 2002, 468.
  (b) Mohapatra, D. K. ; Durugkar, K. A. ARKIVOC 2005, 14, 20.
  (c) Hernadez, J. N. ; Crisostomo, F. R. P. ; Martin, T. ; Martin, V. S. Eur. J. Org. Chem. 2007, 5050.
  (d) Zheng, J. L. ; Yin, B. L. ; Huang, W. M. ; Li, X. P. ; Yao, H. Q. ; Liu, Z. G. ; Zhang, J. C. ; Jiang, S. Tetrahedron Lett. 2009, 50, 5094.
  (e) Lopez-Soria, J. M. ; Perez, S. J. ; Hernandez, J. N. ; Ramirez, M. A. ; Martin, V. S. ; Padron, J. I. RSC. Adv. 2015, 5, 6647.
  (f) Walters, M. A. ; Hoem, A. B. J. Org. Chem. 1994, 59, 2645.
  (g) Hernández, J. N. ; Ramírez, M. A. ; Martín, V. S. J. Org. Chem. 2003, 68, 743.
  (h) Boyle, T. P. ; Bremner, J. B. ; Coates, J. A. ; Keller, P. A. ; Pyne, S. G. Tetrahedron 2005, 61, 7271.
7. [7]
  (a) Hu, X. G. ; Thomas, D. S. ; Griffith, R. ; Hunter, L. Angew. Chem., Int. Ed. 2014, 53, 6176.
  (b) Hu, X. G. ; Lawer, A. ; Peterson, M. B. ; Iranmanesh, H. ; Ball, G. E. ; Hunter, L. Org. Lett. 2016, 18, 662.
  (c) Yan, N. ; Fang, Z. ; Liu, Q. Q. ; Guo, X. H. ; Hu, X. G. Org. Biomol. Chem. 2016, 14, 3469.
  (d) Yan, N. ; Lei, Z. W. ; Su, J. K. ; Liao, W. L. ; Hu, X. G. Chin. Chem. Lett. 2017, 28, 467.
8. [8]
  Xia, J. B.; Zhu, C.; Chen, C. J. Am. Chem. Soc. 2013, 135, 17494. doi: 10.1021/ja410815u
9. [9]
  Comparison of specific rotations was used in Ref. [11] for the same purpose.
10. [10]
  Dey, S.; Garner, P. J. Org. Chem. 2000, 65, 7697. doi: 10.1021/jo000983i
11. [11]
  (a) Liu, J. J. ; Wong, C. H. Tetrahedron Lett. 2002, 43, 4037.
  (b) Shah, S. T. A. ; Singh, S. ; Guiry, P. J. J. Org. Chem. 2009, 74, 2179.
12. [12]
  Navarre, L.; Martinez, R.; Genet, J. P.; Darses, S. J. Am. Chem. Soc. 2008, 130, 6159. doi: 10.1021/ja710691p
13. [13]
  Barrett, A. G. M.; Pilipauskas, D. J. Org. Chem. 1990, 55, 5170. doi: 10.1021/jo00304a035
14. [14]
  Adams, H.; Bawa, R. A.; Jones, S. Org. Biomol. Chem. 2006, 4, 4206. doi: 10.1039/B610055D
15. [15]
  Pandey, R. K.; Dagade, S. P.; Dongare, M. K.; Kumar, P. Synth. Commun. 2003, 33, 4019. doi: 10.1081/SCC-120026337
16. [16]
  Heller, S. T.; Sarpong, R. Org. Lett. 2010, 12, 4572. doi: 10.1021/ol1018882
17. [17]
  Wakasugi, K.; Iida, A.; Misaki, T.; Nishii, Y.; Tanabe, Y. Adv. Synth. Catal. 2003, 345, 1209. doi: 10.1002/(ISSN)1615-4169
18. [18]
  Mandal, P. K.; McMurray, J. S. J. Org. Chem. 2007, 72, 6599. doi: 10.1021/jo0706123
19. [19]
  Burk, M. J.; Allen, J. G. J. Org. Chem. 1997, 62, 7054. doi: 10.1021/jo970903j
20. [20]
  Zheng, J.; Yin, B.; Huang, W.; Li, X.; Yao, H.; Liu, Z.; Zhang, J.; Jiang, S. Tetrahedron Lett. 2009, 50, 5094. doi: 10.1016/j.tetlet.2009.06.104
21. [21]
  Tomita, K.; Oishi, S.; Ohno, H.; Fujii, N. Pept. Sci. 2008, 90, 503. doi: 10.1002/bip.20968
1. [1]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
2. [2]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
3. [3]
  Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO₂ and selectivity over N₂ and CH₄. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659
4. [4]
  Xiujuan Wang , Yijie Wang , Luyun Cui , Wenqiang Gao , Xiao Li , Hong Liu , Weijia Zhou , Jingang Wang . Coordination-based synthesis of Fe single-atom anchored nitrogen-doped carbon nanofibrous membrane for CO₂ electroreduction with nearly 100% CO selectivity. Chinese Chemical Letters, 2024, 35(12): 110031-. doi: 10.1016/j.cclet.2024.110031
5. [5]
  Haixian Ren , Yuting Du , Xiaojing Yang , Fangjun Huo , Le Zhang , Caixia Yin . Development of ESIPT-based specific fluorescent probes for bioactive species based on the protection-deprotection of the hydroxyl. Chinese Chemical Letters, 2025, 36(2): 109867-. doi: 10.1016/j.cclet.2024.109867
6. [6]
  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
7. [7]
  Rui HUANG , Shengjie LIU , Qingyuan WU , Nanfeng ZHENG . Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 201-212. doi: 10.11862/CJIC.20240356
8. [8]
  Shiqi Xu , Zi Ye , Shuang Shang , Fengge Wang , Huan Zhang , Lianguo Chen , Hao Lin , Chen Chen , Fang Hua , Chong-Jing Zhang . Pairs of thiol-substituted 1,2,4-triazole-based isomeric covalent inhibitors with tunable reactivity and selectivity. Chinese Chemical Letters, 2024, 35(7): 109034-. doi: 10.1016/j.cclet.2023.109034
9. [9]
  Caixia Zhu , Qing Hong , Kaiyuan Wang , Yanfei Shen , Songqin Liu , Yuanjian Zhang . Single nanozyme-based colorimetric biosensor for dopamine with enhanced selectivity via reactivity of oxidation intermediates. Chinese Chemical Letters, 2024, 35(10): 109560-. doi: 10.1016/j.cclet.2024.109560
10. [10]
  Shaoming Dong , Yiming Niu , Yinghui Pu , Yongzhao Wang , Bingsen Zhang . Subsurface carbon modification of Ni-Ga for improved selectivity in acetylene hydrogenation reaction. Chinese Chemical Letters, 2024, 35(12): 109525-. doi: 10.1016/j.cclet.2024.109525
11. [11]
  Congyan Liu , Xueyao Zhou , Fei Ye , Bin Jiang , Bo Liu . Confined electric field in nano-sized channels of ionic porous framework towards unique adsorption selectivity. Chinese Chemical Letters, 2025, 36(2): 109969-. doi: 10.1016/j.cclet.2024.109969
12. [12]
  Sanmei Wang , Dengxin Yan , Wenhua Zhang , Liangbing Wang . Graphene-supported isolated platinum atoms and platinum dimers for CO₂ hydrogenation: Catalytic activity and selectivity variations. Chinese Chemical Letters, 2025, 36(4): 110611-. doi: 10.1016/j.cclet.2024.110611
13. [13]
  Lijun Yan , Shiqi Chen , Penglu Wang , Xiangyu Liu , Lupeng Han , Tingting Yan , Yuejin Li , Dengsong Zhang . Hydrothermally stable metal oxide-zeolite composite catalysts for low-temperature NO_x reduction with improved N₂ selectivity. Chinese Chemical Letters, 2024, 35(6): 109132-. doi: 10.1016/j.cclet.2023.109132
14. [14]
  Shanyuan Bi , Jin Zhang , Dengchao Peng , Danhong Cheng , Jianping Zhang , Lupeng Han , Dengsong Zhang . Improved N₂ selectivity for low-temperature NO_x reduction over etched ZSM-5 supported MnCe oxide catalysts. Chinese Chemical Letters, 2025, 36(5): 110295-. doi: 10.1016/j.cclet.2024.110295
15. [15]
  Hua Liu , Jian Zhao , Qi Li , Xiang-Yu Zhang , Zhi-Wei Zheng , Kun Huang , Da-Bin Qin , Bin Zhao . Indium-captured zirconium-porphyrin frameworks displaying rare multi-selectivity for catalytic transfer hydrogenation of aldehydes and ketones. Chinese Chemical Letters, 2025, 36(6): 110593-. doi: 10.1016/j.cclet.2024.110593
16. [16]
  Huimin Luan , Qinming Wu , Jianping Wu , Xiangju Meng , Feng-Shou Xiao . Templates for the synthesis of zeolites. Chinese Journal of Structural Chemistry, 2024, 43(4): 100252-100252. doi: 10.1016/j.cjsc.2024.100252
17. [17]
  Hang Wang , Qi Wang , Chuan-De Wu . Continuous synthesis of ammonia. Chinese Journal of Structural Chemistry, 2025, 44(3): 100437-100437. doi: 10.1016/j.cjsc.2024.100437
18. [18]
  Zhaojun Liu , Zerui Mu , Chuanbo Gao . Alloy nanocrystals: Synthesis paradigms and implications. Chinese Journal of Structural Chemistry, 2023, 42(11): 100156-100156. doi: 10.1016/j.cjsc.2023.100156
19. [19]
  Zhenhao Wang , Yuliang Tang , Ruyu Li , Shuai Tian , Yu Tang , Dehai Li . Bioinspired synthesis of cochlearol B and ganocin A. Chinese Chemical Letters, 2024, 35(7): 109247-. doi: 10.1016/j.cclet.2023.109247
20. [20]
  Hui Jin , Qin Cai , Peiwen Liu , Yan Chen , Derong Wang , Weiping Zhu , Yufang Xu , Xuhong Qian . Multistep continuous flow synthesis of Erlotinib. Chinese Chemical Letters, 2024, 35(4): 108721-. doi: 10.1016/j.cclet.2023.108721

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(791)
HTML views(73)

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