Citation: Song Zhidong, Jiang Lvqi, Yi Wenbin. Fluorodecarboxylation of β, γ-Unsaturated Carboxylic Acids Using Trivalent Iodine and Hydrofluoric Acid-Based Fluorination Reagent[J]. Acta Chimica Sinica, ;2018, 76(12): 967-971. doi: 10.6023/A18080321 shu

Fluorodecarboxylation of β, γ-Unsaturated Carboxylic Acids Using Trivalent Iodine and Hydrofluoric Acid-Based Fluorination Reagent

Chemical Engineering College, Nanjing University of Science and Technology, Nanjing 210094, China

Corresponding author: Yi Wenbin, yiwb@njust.edu.cn
Received Date: 7 August 2018
Available Online: 19 December 2018
Fund Project: the National Natural Science Foundation of China 21476116Natural Science Foundation of Jiangsu Province BK20180476Priority Academic Program Development of Jiangsu Higher Education Institutions the National Natural Science Foundation of China 21776138Fundamental Research Funds for the Central Universities 30916011102Fundamental Research Funds for the Central Universities 30918011314Qing Lan and Six Talent Peaks in Jiangsu Province Project supported by the National Natural Science Foundation of China (Nos. 21776138, 21476116), Fundamental Research Funds for the Central Universities (Nos. 30916011102, 30918011314), Natural Science Foundation of Jiangsu Province (BK20180476), Qing Lan and Six Talent Peaks in Jiangsu Province, Priority Academic Program Development of Jiangsu Higher Education Institutions

Figures(5)

Allylic-substituted compounds serve as versatile building block or the primer for many metal-catalyzed reactions. The introduction of fluorine into a drug molecule will change its pharmacokinetic and pharmacodynamic properties. Therefore, a new method of allylic fluorination would uncover novel synthetic approaches towards highly valuable fluorinated compounds such as inhibitors or fluorine-containing polypropylene. To date, the most reported methods for the synthesis of allylic fluoride involve the use of p-nitrobenzoate or trimethylsilyl as leaving group, or cleavage of tertiary cyclopropyl silyl ethers. In the past decades, the research of fluorodecarboxylation has made great progress. The most reported fluorodecarboxylations involving XeF₂, AgF or AgF₂, Selectfluor, N-fluorodibenzenesulfonimide (NFSI) are often accompanied by the occurrence of oxidation or free radical reactions, which may destroy the terminal olefin structure. The use of the fluoride ion (fluoride salt or hydrofluoric acid) as the nucleophilic component presents a series of challenges, including the low intrinsic nucleophilicity which was demonstrated by its frequent use as an additive to modulate catalytic reactivity or product distribution. However, with the assistance of transition-metal catalyst or organocatalysts, fluoride ion often serve as fluorine source for fluorination of C(sp²)―H and C(sp³)―H. Hypervalent iodine reagents, which have ability to activate a C―C multiple bond, have been recognized as an alternative to noble metal catalyst. Inspired by the pioneering exploration, we sought the possibility of achieving allylic fluorination through simple protocol of fluorodecarboxylation with cheap nucleophilic fluorination reagents and mild oxidant. In this work, a new strategy is introduced for the synthesis of allylic fluorides via decarboxylative fluorination of β, γ-unsaturated carboxylic acids using PhI(OAc)₂ and TEA·3HF. The best result was achieved by using 1.2 equiv. of PhI(OAc)₂ and 5 equiv. of TEA·3HF in CH₂Cl₂ at 75 ℃ for 12 h, giving allylic fluoride 2a in 76% yield. The versatile synthetic utilities of the allylic fluorides were also developed through cycloaddition, oxidation, reduction, substitution involving formation of C―O, C―S, C―Se and C―N bond via activation of C―F bond.
- allylic fluorides,
- decarboxylative fluorination,
- trivalent iodine,
- hydrogen fluoride-based reagent
1. [1]
  (a) Singh, O. V.; Han, H. Org. Lett. 2007, 9, 4801; (b) Mizuno, S.; Terasaki, S.; Shinozawa, T.; Kawatsura, M. Org. Lett. 2017, 19, 504. (c) Wu, R. H.; Yang, W.; Cheng, G.; Li, Y.; Yang, D. Q. Chinese J. Org. Chem. 2016, 36, 2368(in Chinese). (仵瑞华, 杨文, 程果, 李玥, 杨定乔, 有机化学, 2016, 36, 2368); (d) Chen, C. H.; Fu, L.; Chen, P. H.; Liu, G. S. Chin. J. Chem. 2017, 35, 1781; (e) Gu, Y.; Lu, C.; Gu, Y.; Shen, Q. Chin. J. Chem. 2018, 36, 55.
2. [2]
  (a) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, Wiley-VCH, Weinheim, Germany, 2004; (b) Hiyama, T. Organofluorine Compounds: Chemistry and Applications, Springer, Berlin, 2000; (c) Uneyama, K. Organofluorine Chemistry, Blackwell, Oxford, U.K., 2006; (d) Richard, C. Fluorine in Organic Chemistry, CRC Press, Boca Raton, FL, 2004.
3. [3]
  (a) Honda, T.; Liby, K. T.; Su, X.; Sundararajan, C.; Honda, Y.; Suh, N.; Risingsong, R.; Williams, C. R.; Royce, D. B.; Sporn, M. B.; Gribble, G. W. Bioorg. Med. Chem. Lett. 2006, 16, 6306; (b) Kaneko, S.; Arai, M.; Uchida, T.; Harasaki, T.; Fukuoka, T.; Konosu, T. Bioorg. Med. Chem. Lett. 2002, 12, 1705; (c) Rothman, S. C.; Johnston, J. B.; Lee, S.; Walker, J. R.; Poulter, C. D. J. Am. Chem. Soc. 2008, 130, 4906; (d) Leblanc, Y.; Roy, P.; Leger, S.; Grimm, E.; Wang, Z. WO 9841516, 1998[Chem. Abstr. 1998, 129, 275831].
4. [4]
  (a) Walkowiak-Kulikowska, J.; Szwajca, A.; Boschet, F.; Gouverneur, V.; Ameduri, B. Macromolecules 2014, 47, 8634. (b) Kostov, G.; Tredwell, M.; Gouverneur, V.; Ameduri, B. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 3843. (c) Wall, L. A. Fluoropolymers, Wiley, New York, 1972.
5. [5]
  Hollingworth, C.; Hazari, A.; Hopkinson, M. N.; Tredwell, M.; Benedetto, E.; Huiban, M.; Gee, A. D.; Brown, J. M.; Gouverneur, V. Angew. Chem., Int. Ed. 2011, 50, 2613. doi: 10.1002/anie.201007307
6. [6]
  Walkowiak, J.; Martinez, D. C. T.; Ameduri, B.; Gouverneur, V. Synthesis 2010, 1883.
7. [7]
  (a) Kirihara, M.; Kambayashi, T.; Momose, T. Chem. Commun. 1996, 1103; (b) Kirihara, M.; Kakuda, H.; Tsunooka, M.; Shimajiri, A.; Takuwa, T.; Hatano, A. Tetrahedron Lett. 2003, 44, 8513.
8. [8]
  Hu, J. B.; He, Z. B. CN 102219638, 2011[Chem. Abstr. 2011, 155, 588760].
9. [9]
  (a) He, Z. B.; Ping, T.; Hu, J. B. Org. Lett. 2016, 18, 72; (b) Ma, J. J.; Yi, W. B.; Lu, G. P.; Cai, C. Adv. Synth. Catal. 2015, 357, 3447. (c) Xu, X. L.; Chen, H. H.; He, J. B.; Xu, H. J. Chin. J. Chem. 2017, 35, 1665; (d) Montazerozohori, M.; Nasr-Esfahani, M.; Akhlaghi, P. Chin. J. Chem. 2009, 27, 1007; (e) Zhang, J. J.; Cheng, Y. B.; Duan, X. H. Chin. J. Chem. 2017, 35, 311; (f) Zhao, Y. W.; Feng, Q.; Song, Q. L. Chin. Chem. Lett. 2016, 27, 571.
10. [10]
  (a) Chatalova-Sazepin, C.; Binayeva, M.; Epifanov, M.; Zhang, W.; Foth, P.; Amador, C.; Jagdeo, M.; Boswell, B. R.; Sammis, G. M. Org. Lett. 2016, 18, 4570; (b) Patrick, T. B.; Khazaeli, S.; Nadji, S.; Hering-Smith, K.; Reif, D. J. Org. Chem. 1993, 58, 705.
11. [11]
  (a) Yin, F.; Wang, Z.; Li, Z.; Li, C. J. Am. Chem. Soc. 2012, 134, 10401; (b) Zhang, X. Comput. Theor. Chem. 2016, 1082, 11; (c) Zhang, Q. W.; Brusoe, A. T.; Mascitti, V.; Hesp, K. D.; Blakemore, D. C.; Kohrt, J. T.; Hartwig, J. F. Angew. Chem., Int. Ed. 2016, 55, 9758; (d) Mizuta, S.; Stenhagen, I. S. R.; O'Duill, M.; Wolstenhulme, J.; Kirjavainen, A. K.; Forsback, S. J.; Tredwell, M.; Sandford, G.; Moore, P. R.; Huiban, M.; Luthra, S. K.; Passchier, J.; Solin, O.; Gouverneur, V. Org. Lett. 2013, 15, 2648.
12. [12]
  (a) Leung, J. C. T.; Chatalova-Sazepin, C.; West, J. G.; Rueda-Becerril, M.; Paquin, J. F.; Sammis, G. M. Angew. Chem., Int. Ed. 2012, 51, 10804; (b) Leung, J. C. T.; Sammis, G. M. Eur. J. Org. Chem. 2015, 2197; (c) Ventre, S.; Petronijevic, F. R.; MacMillan, D. W. C. J. Am. Chem. Soc. 2015, 137, 5654; (d) Wang, D. H.; Yuan, Z. L.; Liu, Q. L.; Chen, P. H. Liu, G. S. Chin. J. Chem. 2018, 36, 507; (e) Dong, Y.; Wang, Z.; Li, C. Nat. Commun. 2017, 8, 277.
13. [13]
  Rueda-Becerril, M.; Chatalova Sazepin, C.; Leung, J. C. T.; Okbinoglu, T.; Kennepohl, P.; Paquin, J. F.; Sammis, G. M. J. Am. Chem. Soc. 2012, 134, 4026. doi: 10.1021/ja211679v
14. [14]
  Yang, Q.; Mao, L. L.; Yang, B.; Yang, S. D. Org. Lett. 2014, 16, 3460. doi: 10.1021/ol501357w
15. [15]
  (a) Fagnou, K.; Lautens, M. Angew. Chem. 2002, 114, 26; (b) Yan, N.; Lei, Z. W.; Su, J. K.; Liao, W. L. Hu, X. G. Chin. Chem. Lett. 2017, 28, 467; (c) Wang, L. Y.; Jiang, X. H.; Tang, P. P. Org. Chem. Front. 2017, 4, 1958.
16. [16]
  (a) Katcher, M. H.; Sha, A.; Doyle, A. G. J. Am. Chem. Soc. 2011, 133, 15902; (b) Lee, E.; Hooker, J. M.; Ritter, T. J. Am. Chem. Soc. 2012, 134, 17456; (c) Fier, P. S.; Luo, J.; Hartwig, J. F. J. Am. Chem. Soc. 2013, 135, 2552; (d) Fier, P. S.; Hartwig, J. F. J. Am. Chem. Soc. 2012, 134, 10795; (e) Liu, Z.; Chen, H.; Lv, Y.; Tan, X.; Shen, H.; Yu, H.-Z.; Li, C. J. Am. Chem. Soc. 2018, 140, 6169; (f) Ma, J. A.; Li, S. Org. Chem. Front. 2014, 1, 712.
17. [17]
  Woerly, E. M.; Banik, S. M.; Jacobsen, E. N. J. Am. Chem. Soc. 2016, 138, 13858. doi: 10.1021/jacs.6b09499
18. [18]
  Huang, X.; Liu, W.; Hooker, J. M.; Groves, J. T. Angew. Chem., Int. Ed. 2015, 54, 5241. doi: 10.1002/anie.v54.17
19. [19]
  (a) Souto, J. A.; Becker, P.; Iglesias, A.; Muñiz, K. J. Am. Chem. Soc. 2012, 134, 15505; (b) Souto, J. A.; Martínez, C.; Velilla, I.; Muñiz, K. Angew. Chem., Int. Ed. 2013, 52, 324; (c) Röben, C.; Souto, J. A.; Escudero-Adán, E. C.; Muñiz, K. Org. Lett. 2013, 15, 1008; (d) Farid, U.; Malmedy, F.; Claveau, R.; Albers, L.; Wirth, T. Angew. Chem., Int. Ed. 2013, 52, 7018; (e) Wang, Y.; Wang, Y.; Zhang, Q.; Li, D. Org. Chem. Front. 2017, 4, 514; (f) Gao, P.; Fan, M. J.; Bai, Z. J.; Wei, Y. Y. Chin. J. Chem. 2015, 33, 479.
20. [20]
  (a) Kiyokawa, K.; Yahata, S.; Kojima, T.; Minakata, S. Org. Lett. 2014, 16, 4646; (b) Kiyokawa, K.; Kojima, T.; Hishikawa, Y.; Minakata, S. Chem. Eur. J. 2015, 21, 15548.
21. [21]
  (a) Jiang, L. Q.; Qian, J. L.; Yi, W. B.; Lu, G. P.; Cai, C.; Zhang, W. Angew. Chem., Int. Ed. 2015, 54, 14965; (b) Lin, Y.-M.; Yi, W. B.; Shen, W. Z.; Lu, G. P. Org. Lett. 2016, 18, 592; (c) Song, Z. D.; Yi, W. B. Adv. Synth. Catal. 2016, 358, 2727.
22. [22]
  (a) Kitamura, T.; Muta, K.; Kuriki, S. Tetrahedron Lett. 2013, 54, 6118; (b) Carpenter, W. J. Org. Chem. 1966, 31, 2688; (c) Zupan, M.; Pollak, A. J. Fluorine Chem. 1976, 7, 445; (d) Arrica, M. A.; Wirth, T. Eur. J. Org. Chem. 2005, 395; (e) Ye, C.; Twamley, B.; Shreeve, J. M. Org. Lett. 2005, 7, 3961.
23. [23]
  Kitamura, T.; Muta, K.; Oyamada, J. J. Org. Chem. 2015, 80, 10431. doi: 10.1021/acs.joc.5b01929
24. [24]
  Nash, T. J.; Pattison, G. Eur. J. Org. Chem. 2015, 3779.
25. [25]
  Li, Y.; Ni, C.; Liu, J.; Zhang, L.; Zheng, J.; Zhu, L.; Hu, J. B. Org. Lett. 2006, 8, 1693. doi: 10.1021/ol060322t
26. [26]
  (a) Fukuzumi, T.; Shibata, N.; Sugiura, M.; Yasui, H.; Nakamura, S.; Toru, T. Angew. Chem., Int. Ed. 2006, 45, 4973; (b) Furukawa, T.; Shibata, N.; Mizuta, S.; Nakamura, S.; Toru, T.; Shiro, M. Angew. Chem., Int. Ed. 2008, 47, 8051.
27. [27]
  Prakash, G. K. S.; Ledneczki, I.; Chacko, S.; Olah, G. A. Org. Lett. 2008, 10, 557. doi: 10.1021/ol702500u
28. [28]
  Traff, A. M.; Janjetovic, M.; Ta, L.; Hilmersson, G. Angew. Chem., Int. Ed. 2013, 52, 12073. doi: 10.1002/anie.201306104
29. [29]
  (a) Yi, W. B.; Huang, X.; Zhang, Z.; Zhu, D.; Cai, C.; Zhang, W. Green Chem. 2012, 14, 3185; (b) Qian, J. L.; Yi, W. B.; Huang, X.; Miao, Y. B.; Zhang, J. K.; Cai, C.; Zhang, W. Org. Lett. 2015, 17, 1090; (c) Song, Z. D.; Huang, X.; Yi, W. B.; Zhang, W. Org. Lett. 2016, 18, 5640.
30. [30]
  Benedetto, E.; Keita, M.; Tredwell, M.; Hollingworth, C.; Brown, J. M.; Gouverneur, V. Organometallics 2012, 31, 1408.
1. [1]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
2. [2]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
3. [3]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
4. [4]
  Yuanpei ZHANG , Jiahong WANG , Jinming HUANG , Zhi HU . Preparation of magnetic mesoporous carbon loaded nano zero-valent iron for removal of Cr(Ⅲ) organic complexes from high-salt wastewater. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1731-1742. doi: 10.11862/CJIC.20240077
5. [5]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
6. [6]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
7. [7]
  Ruiqing LIU , Wenxiu LIU , Kun XIE , Yiran LIU , Hui CHENG , Xiaoyu WANG , Chenxu TIAN , Xiujing LIN , Xiaomiao FENG . Three-dimensional porous titanium nitride as a highly efficient sulfur host. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 867-876. doi: 10.11862/CJIC.20230441
8. [8]
  Qilu DU , Li ZHAO , Peng NIE , Bo XU . Synthesis and characterization of osmium-germyl complexes stabilized by triphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1088-1094. doi: 10.11862/CJIC.20240006
9. [9]
  Wendian XIE , Yuehua LONG , Jianyang XIE , Liqun XING , Shixiong SHE , Yan YANG , Zhihao HUANG . Preparation and ion separation performance of oligoether chains enriched covalent organic framework membrane. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1528-1536. doi: 10.11862/CJIC.20240050
10. [10]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
11. [11]
  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
12. [12]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
13. [13]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
14. [14]
  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
15. [15]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
16. [16]
  Hao BAI , Weizhi JI , Jinyan CHEN , Hongji LI , Mingji LI . Preparation of Cu₂O/Cu-vertical graphene microelectrode and detection of uric acid/electroencephalogram. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1309-1319. doi: 10.11862/CJIC.20240001
17. [17]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(1390)
HTML views(197)

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