Citation: Li Shu-Sen, Wang Jianbo. Recent Advance in Asymmetric Trifluoromethylthiolation[J]. Acta Chimica Sinica, ;2018, 76(12): 913-924. doi: 10.6023/A18070306 shu

Recent Advance in Asymmetric Trifluoromethylthiolation

Li Shu-Sen ^a ,
Wang Jianbo ^a,b,,

a.
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Wang Jianbo, wangjb@pku.edu.cn
Received Date: 30 July 2018
Available Online: 29 December 2018
Fund Project: the National Basic Research Program of China 2015CB856600Project supported by the National Natural Science Foundation of China (No. 21332002) and the National Basic Research Program of China (973 Program, No. 2015CB856600)the National Natural Science Foundation of China 21332002the National Basic Research Program of China 973 Program

Figures(17)

Fluorine-containing groups can modulate the physicochemical and biological properties of organic molecules. Consequently, the synthesis of fluorinated organic molecules has attracted considerable attention in the field of pharmaceuticals, agrochemicals and material sciences. Among fluorine-containing groups, the trifluoromethylthio group has the highest Hansch's hydrophobicity parameter and remarkable electron-withdrawing character. The incorporation of a trifluoromethylthio group into organic molecules can significantly enhance their membrane permeability and metabolic stability because of its high lipophilicity and strong electron-withdrawing effect. As a result, various methods have been involved to synthesize SCF₃-containing compounds using electrophilic or nucleophilic trifluoromethylthio reagents. On the other hand, the chirality of pharmaceutical molecules has an important effect on their properties, and different stereoisomers of a pharmaceutical molecules always have dramatically different pharmaceutical activities. Thus, the asymmetric trifluoromethylthiolation of organic molecules is of growing interest in recent years. Up to now, this field is still in the stage of initial development. In this perspective article, we will briefly summarize the methods of asymmetric trifluoromethylthiolation of organic molecules that have been reported so far. Two different strategies including the use of electrophilic trifluoromethylthiolating reagents and the use of trifluoromethylthio-containing building blocks will be introduced. Employing electrophilic trifluoromethylthiolating reagents, the enantioselective trifluoromethylthiolation of β-ketoesters, oxindoles as well as alkenes have been developed using Cinchona alkaloid, copper(Ⅱ) or indane-based chiral sulfide/selenide as the catalyst. Alternatively, using trifluoromethylthiolated building blocks is another approach to establish chiral centers bearing the trifluoromethylthio group. In this approach, an asymmetric trifluoromethylthiolation via enantioselective ^{[2, 3]}-sigmatropic rearrangement of a sulfonium ylide generated from SCF₃-containing sulfide and metal carbene has been disclosed using chiral Rh(Ⅱ) and Cu(Ⅰ) as the catalyst. Finally, we will discuss the challenges of the asymmetric trifluoromethylthiolation of organic molecules in the future.
- trifluoromethylthiolation,
- asymmetric catalysis,
- organofluorine compounds,
- stereoselectivity,
- organic synthesis
1. [1]
  (a) Hagmann, W. K. J. Med. Chem. 2008, 51, 4359. (b) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320. (c) Manteau, B.; Pazenok, S.; Vors, J.-P.; Leroux, F. R. J. Fluorine Chem. 2010, 131, 140. (d) Gillis, E. P.; Eastman, K. J.; Hill, M. D.; Donnelly, D. J.; Meanwell, N. A. J. Med. Chem. 2015, 58, 8315.
2. [2]
  (a) Leo, A.; Hansch, C.; Elkins, D. Chem. Rev. 1971, 71, 525. (b) Hansch, C.; Leo, A.; Unger, S. H.; Kim, K. H.; Nikaitani, D.; Lien, E. J. J. Med. Chem. 1973, 16, 1207.
3. [3]
  For recent reviews on trifluoromethylthiolation, see: (a) Toulgoat, F.; Alazet, S.; Billard, T. Eur. J. Org. Chem. 2014, 2014, 2415. (b) Shao, X.; Xu, C.; Lu, L.; Shen, Q. Acc. Chem. Res. 2015, 48, 1227. (c) Xu, X.-H.; Matsuzaki, K.; Shibata, N. Chem. Rev. 2015, 115, 731. (d) Zhang, K.; Xu, X.; Qing, F. Chin. J. Org. Chem. 2015, 35, 556(in Chinese). (张柯, 徐修华, 卿凤翎, 有机化学, 2015, 35, 556.) (e) Xu, J.; Chen, P.; Ye, J.; Liu, G. Acta Chim. Sinica 2015, 73, 1294(in Chinese). (徐佳斌, 陈品红, 叶金星, 刘国生, 化学学报, 2015, 73, 1294.) (f) Zheng, H.; Huang, Y.; Weng, Z. Tetrahedron Lett. 2016, 57, 1397. (g) Li, G.; Sun, D. Chin. J. Org. Chem. 2016, 36, 1715(in Chinese). (李恭铭, 孙德群, 有机化学, 2016, 36, 1715). (h) Barata-Vallejo, S.; Bonesi, S.; Postigo, A. Org. Biomol. Chem. 2016, 14, 7150. (i) Guo, Y.; Huang, M.-W.; Fu, X.-L.; Liu, C.; Chen, Q.-Y.; Zhao, Z.-G.; Zeng, B.-Z.; Chen, J. Chin. Chem. Lett. 2017, 28, 719. (j) 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.)(k)Zhao, X.; Li, T.; Tian, M.; Su, Z.; Wei, A.; Lu, K. Chin. J. Org. Chem. 2018, 38, 677(in Chinese). (赵霞, 李天骄, 田苗苗, 苏志扬, 魏奥琪, 芦逵, 有机化学, 2018, 38, 677.)
4. [4]
  Bootwicha, T.; Liu, X.; Pluta, R.; Atodiresei, I.; Rueping, M. Angew. Chem., Int. Ed. 2013, 52, 12856. doi: 10.1002/anie.201304957
5. [5]
  Wang, X.; Yang, T.; Cheng, X.; Shen, Q. Angew. Chem., Int. Ed. 2013, 52, 12860. doi: 10.1002/anie.201305075
6. [6]
  Rueping, M.; Liu, X.; Bootwicha, T.; Pluta, R.; Merkens, C. Chem. Commun. 2014, 50, 2508. doi: 10.1039/c3cc49877h
7. [7]
  Zhu, X.-L.; Xu, J.-H.; Cheng, D.-J.; Zhao, L.-J.; Liu, X.-Y.; Tan, B. Org. Lett. 2014, 16, 2192. doi: 10.1021/ol5006888
8. [8]
  Yang, T.; Shen, Q.; Lu, L. Chin. J. Chem. 2014, 32, 678. doi: 10.1002/cjoc.201400392
9. [9]
  Liao, K.; Zhou, F.; Yu, J.-S.; Gao, W.-M.; Zhou, J. Chem. Commun. 2015, 51, 16255. doi: 10.1039/C5CC07010D
10. [10]
  Zhao, B.-L.; Du, D.-M. Org. Lett. 2017, 19, 1036. doi: 10.1021/acs.orglett.6b03846
11. [11]
  Li, M.; Xue, X.-S.; Cheng, J.-P. ACS Catal. 2017, 7, 7977. doi: 10.1021/acscatal.7b03007
12. [12]
  Deng, Q.-H.; Rettenmeier, C.; Wadepohl, H.; Gade, L. H. Chem.-Eur. J. 2014, 20, 93. doi: 10.1002/chem.201303641
13. [13]
  Jin, M. Y.; Li, J.; Huang, R.; Zhou, Y.; Chung, L. W.; Wang, J. Chem. Commun. 2018, 54, 4581. doi: 10.1039/C8CC02097C
14. [14]
  Zhang, H.; Leng, X.; Wan, X.; Shen, Q. Org. Chem. Front. 2017, 4, 1051. doi: 10.1039/C7QO00042A
15. [15]
  Chachignon, H.; Kondrashov, E. V.; Cahard, D. Adv. Synth. Catal. 2018, 360, 965. doi: 10.1002/adsc.v360.5
16. [16]
  Liu, X.; An, R.; Zhang, X.; Luo, J.; Zhao, X. Angew. Chem., Int. Ed. 2016, 55, 5846. doi: 10.1002/anie.201601713
17. [17]
  Luo, J.; Liu, Y.; Zhao, X. Org. Lett. 2017, 19, 3434. doi: 10.1021/acs.orglett.7b01392
18. [18]
  Luo, J.; Cao, Q.; Cao, X.; Zhao, X. Nat. Commun. 2018, 9, 527. doi: 10.1038/s41467-018-02955-0
19. [19]
  Liu, X.; Liang, Y.; Ji, J.; Luo, J.; Zhao, X. J. Am. Chem. Soc. 2018, 140, 4782. doi: 10.1021/jacs.8b01513
20. [20]
  Zhang, Z.; Sheng, Z.; Yu, W.; Wu, G.; Zhang, R.; Chu, W.-D.; Zhang, Y.; Wang, J. Nat. Chem. 2017, 9, 970. doi: 10.1038/nchem.2789
21. [21]
  Xu, L.; Wang, H.; Zheng, C.; Zhao, G. Adv. Synth. Catal. 2017, 359, 2942. doi: 10.1002/adsc.v359.17
22. [22]
  Hock, K. J.; Koenigs, R. M. Angew. Chem., Int. Ed. 2017, 56, 13566. doi: 10.1002/anie.201707092
23. [23]
  Mao, G.; Chen, L.; Wang, C. Sci. China Chem. 2017, 60, 1565. doi: 10.1007/s11426-017-9113-5
1. [1]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
2. [2]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
3. [3]
  Aidang Lu , Yunting Liu , Yanjun Jiang . Comprehensive Organic Chemistry Experiment: Synthesis and Characterization of Triazolopyrimidine Compounds. University Chemistry, 2024, 39(8): 241-246. doi: 10.3866/PKU.DXHX202401029
4. [4]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
5. [5]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
6. [6]
  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
7. [7]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
8. [8]
  Qianlang Wang , Jijun Sun , Qian Chen , Quanqin Zhao , Baojuan Xi . The Appeal of Organophosphorus Compounds: Clearing Their Name. University Chemistry, 2025, 40(4): 299-306. doi: 10.12461/PKU.DXHX202405205
9. [9]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
10. [10]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
11. [11]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
12. [12]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181
13. [13]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
14. [14]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . 碳基催化剂催化有机液体氢载体脱氢研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-. doi: 10.1016/j.actphy.2024.100044
15. [15]
  Wenjie SHI , Fan LU , Mengwei CHEN , Jin WANG , Yingfeng HAN . Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360
16. [16]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
17. [17]
  Hong CAI , Jiewen WU , Jingyun LI , Lixian CHEN , Siqi XIAO , Dan LI . Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 114-122. doi: 10.11862/CJIC.20240382
18. [18]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
19. [19]
  .
  CCS Chemistry 综述推荐│绿色氧化新思路：光/电催化助力有机物高效升级
  . CCS Chemistry, 2025, 7(10.31635/ccschem.024.202405369): -.
20. [20]
  Zelong LIANG , Shijia QIN , Pengfei GUO , Hang XU , Bin ZHAO . Synthesis and electrocatalytic CO₂ reduction performance of metal-organic framework catalysts loaded with silver particles. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 165-173. doi: 10.11862/CJIC.20240409

Get Citation

PDF

XML

Metrics

PDF Downloads(39)
Abstract views(1946)
HTML views(406)

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