Application of Benzylic C-H Fluorination for the Formal Synthesis of syn-α, β-Difluoro-γ-amino Acid

doi:10.6023/cjoc201712020

Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (6): 1525-1529.DOI: 10.6023/cjoc201712020 Previous Articles Next Articles

Articles

应用苄位C—H氟化形式合成α,β-二氟代-γ-氨基酸

刘清泉, 胡祥国

江西师范大学国家单糖化学合成工程技术研究中心南昌 330022

收稿日期:2017-12-13 修回日期:2018-01-19 发布日期:2018-02-06
通讯作者: 胡祥国,E-mail:huxiangg@iccas.ac.cn E-mail:huxiangg@iccas.ac.cn
基金资助:
国家自然科学基金（No.21502076）、江西省杰出青年资助计划（No.20171BCB23039）.

Application of Benzylic C-H Fluorination for the Formal Synthesis of syn-α, β-Difluoro-γ-amino Acid

Liu Qingquan, Hu Xiangguo

National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022

Received:2017-12-13 Revised:2018-01-19 Published:2018-02-06
Contact: 10.6023/cjoc201712020 E-mail:huxiangg@iccas.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21502076) and the Outstanding Young Talents Scheme of Jiangxi Province (No. 20171BCB23039).

1. Application of Benzylic C-H Fluorination for the Formal Synthesis of syn-α, β-Difluoro-γ-amino Acid.PDF(1586KB)

Abstract

Benzylic C-H fluorination has emerged as a valuable tool for the introduction of fluorine. However, the powerfulness of benzylic C-H fluorination has not been tested in any multi-step synthesis. α,β-Difluoro-γ-amino acids are useful entities for biological application owing to the so-called fluorine conformational effect. In this work, benzylic C-H fluorination has been successfully utilized as the key step for the formal synthesis of syn-α,β-difluoro-γ-amino acid 1, a very challenging but useful target. The approach developed in this work could be viewed as more practical compared to the previous one, because:(1) no corrosive and toxic nucleophilic fluorinating reagents are used, (2) the overall yield is 18% (the previous approach is about 5%), and (3) the key benzylic C-H reaction developed by Chen and co-workers was scaled up to one gram without decreasing its original efficiency. A striking fluorine effect was observed:a carbon with one fluorine atom on the adjacent carbon is much less reactive than an ordinary carbon for the benzylic C-H fluorination.

Key words: C-H fluorination, organofluorine, amino acid

Cite this article

Liu Qingquan, Hu Xiangguo. Application of Benzylic C-H Fluorination for the Formal Synthesis of syn-α, β-Difluoro-γ-amino Acid[J]. Chin. J. Org. Chem., 2018, 38(6): 1525-1529.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Champagne, P. A.; Desroches, J.; Hamel, J. D.; Vandamme, M.; Paquin, J. F. Chem.Rev. 2015, 115, 9073.
(b) Rong, J.; Ni, C.; Wang, Y.; Kuang, C.; Gu, Y.; Hu, J. Acta Chim. Sinica 2017, 75, 105(in Chinese). (荣健, 倪传法, 王云泽, 匡翠文, 顾玉诚, 胡金波, 化学学报, 2017, 75, 1, 105.)
(c) Zhang, P.; Lu, L.; Shen, Q. Acta Chim.Sinica 2017, 75, 744(in Chinese). (张盼盼, 吕龙, 沈其龙, 化学学报, 2017, 75, 744.)
(d) He, J.; Lou, S.; Xu, D. Chin.J.Org.Chem. 2016, 36, 1218(in Chinese). (何将旗, 娄绍杰, 许丹倩, 有机化学, 2016, 36, 1218.)
(e) Gu, Y.; Lu, C.; Gu, Y.; Shen, Q. Chin.J.Chem. 2018, 36, 55.
[2] Koperniku, A.; Liu, H.; Hurley, P. B. Eur.J.Org. Chem. 2016, 871.
[3] Bloom, S.; Pitts, C. R.; Miller, D. C.; Haselton, N.; Holl, M. G.; Urheim, E.; Lectka, T. Angew.Chem., Int.Ed. 2012, 51, 10580.
[4] Pitts, C. R.; Bloom, S.; Woltornist, R.; Auvenshine, D. J.; Ryzhkov, L. R.; Siegler, M. A.; Lectka, T. J.Am.Chem.Soc. 2014, 136, 9780.
[5] Bloom, S.; Pitts, C. R.; Woltornist, R.; Griswold, A.; Holl, M. G.; Lectka, T. Org.Lett. 2013, 15, 1722.
[6] Bloom, S.; Sharber, S. A.; Holl, M. G.; Knippel, J. L.; Lectka, T. J. Org.Chem. 2013, 78, 11082.
[7] Liu, W.; Groves, J. T. Angew.Chem., Int.Ed. 2013, 52, 6024.
[8] Amaoka, Y.; Nagatomo, M.; Inoue, M. Org.Lett. 2013, 15, 2160.
[9] Xu, P.; Guo, S.; Wang, L.; Tang, P. Angew.Chem., Int. Ed. 2014, 53, 5955.
[10] Nodwell, M. B.; Bagai, A.; Halperin, S. D.; Martin, R. E.; Knust, H.; Britton, R. Chem.Commun. 2015, 51, 11783.
[11] Xia, J.-B.; Zhu, C.; Chen, C. J.Am. Chem.Soc. 2013, 135, 17494.
[12] Bloom, S.; Knippel, J. L.; Lectka, T. Chem. Sci. 2014, 5, 1175.
[13] Bloom, S.; McCann, M.; Lectka, T. Org.Lett. 2014, 16, 6338.
[14] Cantillo, D.; de Frutos, O.; Rincon, J. A.; Mateos, C.; Kappe, C. O. J.Org.Chem. 2014, 79, 8486.
[15] Ma, J.-J.; Yi, W.-B.; Lu, G.-P.; Cai, C. Org. Biomol.Chem. 2015, 13, 2890.
[16] Huang, X.; Liu, W.; Ren, H.; Neelamegam, R.; Hooker, J. M.; Groves, J. T. J.Am.Chem.Soc. 2014, 136, 6842.
[17] Carroll, L.; Evans, H. L.; Spivey, A. C.; Aboagye, E. O. Chem.Commun. 2015, 51, 8439.
[18] Zimmer, L. E.; Sparr, C.; Gilmour, R. Angew. Chem., Int.Ed. 2011, 50, 11860.
[19] Hunter, L. Beilstein J.Org.Chem. 2010, 6.
[20] O'Hagan, D. Chem.Soc.Rev. 2008, 37, 308.
[21] (a) Hunter, L.; Jolliffe, K. A.; Jordan, M. J. T.; Jensen, P.; Macquart, R. B. Chem.-Eur. J. 2011, 17, 2340.
(b) Yamamoto, I.; Jordan, M. J. T.; Gavande, N.; Doddareddy, M. R.; Chebib, M.; Hunter, L. Chem.Commun. 2012, 48, 829.
[22] Hu, X. G.; Thomas, D. S.; Griffith, R.; Hunter, L. Angew.Chem.Int.Ed. 2014, 53, 6176.
[23] Hunter, L.; Butler, S.; Ludbrook, S. B. Org. Biomol.Chem. 2012, 10, 8911.
[24] Patel, A. R.; Hu, X. G.; Lawer, A.; Ahmed, M. I.; Au, C.; Jwad, R.; Trinh, J.; Gonzalez, C.; Hannah, E.; Bhadbhade, M. M.; Hunter, L. Tetrahedron 2016, 72, 3305.
[25] Beeson, T. D.; MacMillan, D. W. C. J.Am. Chem.Soc. 2005, 127, 8826.
[26] Steiner, D. D.; Mase, N.; Barbas, C. F. Angew. Chem., Int.Ed. 2005, 44, 3706.
[27] Marigo, M.; Fielenbach, D. I.; Braunton, A.; Kjoersgaard, A.; Jorgensen, K. A. Angew.Chem., Int.Ed. 2005, 44, 3703.
[28] Fadeyi, O. O.; Lindsley, C. W. Org.Lett. 2009, 11, 943.
[29] (a) Ni, C. F.; Hu, J. B. Chem.Soc. Rev. 2016, 45, 5441.
(b) Ni, C. F.; Hu, M. Y.; Hu, J. B. Chem.Rev. 2015, 115, 765.
[30] (a) Ni, C.; Li, Y.; Hu, J. J.Org.Chem. 2006, 71, 6829.
(b) Zhang, W.; Ni, C.; Hu, J. Top.Curr.Chem. 2012, 308, 25.
[31] Ma, H.; Chen, G.; Wang, T.; Li, Q.; Liu, Y. Chem. Biol.Drug Des. 2016, 88, 363.

应用苄位C—H氟化形式合成α,β-二氟代-γ-氨基酸

Application of Benzylic C-H Fluorination for the Formal Synthesis of syn-α, β-Difluoro-γ-amino Acid

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Haoruo Shangguan, Ping Huang, Zhenya Dai, Ping Wang. Synthesis and Application of β-Thiolated Amino Acids [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3089-3097.
[2]	Zhangtao Zhou, Yang Wang, Bingxin Cheng, Weiping Ye. [RuCl(p-cymene)-(S)-BINAP]Cl Catalyzed Asymmetric Preparation of trans-3-Amino-bicyclo[2.2.2]octane-2-carboxylic Acid Ethyl Ester [J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2961-2967.
[3]	Sifan Dong, Haolong Li, Yuan Qin, Shiming Fan, Shouxin Liu. Research Progress of Amino Acids as Transient Directing Groups in C—H Bond Activation Reactions [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2351-2367.
[4]	Yongling Wang, Tiexin Zhang, Xuming Zhang, Hanyang Sun, Jinyao Leng, Yaming Li. Synthesis of Unnatural Amino Acid Derivatives by Visible- Light-Catalyzed Decarboxylative Alkylation of N-Aromatic Glyoxylimines [J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4284-4293.
[5]	Na Li, Xiaofeng Tan, Qinglai Yang. Recent Progress on Strategies and Applications of Imaging for Intestinal Microflora [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1375-1386.
[6]	Jiayu Hu, Zhiqiang Zhu, Zongbo Xie, Zhanggao Le. Recent Advances in Visible-Light-Induced Decarboxylative Coupling Reactions of α-Amino Acid Derivatives [J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 978-1001.
[7]	Mengmeng Guo, Zilun Yu, Yulan Chen, Danhua Ge, Mengtao Ma, Zhiliang Shen, Xueqiang Chu. Difluorinated Silyl Enol Ethers as Fluorine-Containing Building Blocks for the Synthesis of Organofluorine Compounds [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3562-3587.
[8]	Ting Wang, Jingchao Chen, Lun Wang, Zheting Wang, Baomin Fan. Asymmetric Transfer Hydrogenation of α-Aryl Amidates Using Methanol as Hydrogen Source [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3693-3703.
[9]	Nana Wang, Jingcheng Xu, Haibo Mei, Hiroki Moriwaki, Kunisuke Izawa, Vadim A. Soloshonok, Jianlin Han. Electrochemical Approaches for Preparation of Tailor-Made Amino Acids [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3034-3049.
[10]	Li Sheng, Haoling Gao, Xufeng Wu, Gang Fan, Pengcheng Liu. Rhodium/(2S,2'S,3S,3'S)-3,3'-Di-tert-butyl-4,4'-dimethoxy-2,2',3,3'-tetrahydro-2,2'-bibenzo[d][1,3]oxaphosphole (MeO-BIBOP) Catalyzed Synthesis of (R)-3-tert-Butoxy-carbonylamino-4-(2,4,5-trifluorophenyl)butyric Acid by Asymmetric Reduction of Enamines [J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 2105-2111.
[11]	Qin Chengyuan, Liu Wei, Nie Yong, Gao Ying, Miao Jinling, Li Tianrui, Jiang Xuchuan. Advances in Organofluorine Compounds with Aggregation-Induced Emission [J]. Chinese Journal of Organic Chemistry, 2020, 40(8): 2232-2253.
[12]	Wei Liang, Xiao Lu, Hu Yuanzheng, Wang Zuofei, Tao Haiyan, Wang Chunjiang. Recent Advances in Metallated Azomethine Ylides for the Synthesis of Chiral Unnatural α-Amino Acids [J]. Chin. J. Org. Chem., 2019, 39(8): 2119-2130.
[13]	Gao Sufan, Zhang Yanchun, Li Jiaming, Zhang Bin, Yang Yu, Hu Mengqi. Synthesis and Biological Evaluation of Novel Phenylpropenoyl-amino Acid Derivatives [J]. Chin. J. Org. Chem., 2019, 39(7): 1953-1961.
[14]	Zhou Anxi, Zhou Xiaofei, Mao Liuliang, Zheng Dagui, Zhu Xianhong, Chen Zongbao. Copper-Catalyzed Oxidative Cross-Coupling Reactions for the Synthesis of β-Acyl-α-amino Acid Derivatives in Aqueous Medium [J]. Chin. J. Org. Chem., 2019, 39(4): 1070-1078.
[15]	Liu Chuan-Zhi, Wang Hui, Zhang Dan-Wei, Zhao Xin, Li Zhan-Ting. Study on Halogen Bonding of Organofluorine Compounds in China [J]. Chin. J. Org. Chem., 2019, 39(1): 28-37.