Recent Advance in Asymmetric Trifluoromethylthiolation

doi:10.6023/A18070306

Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (12): 913-924.DOI: 10.6023/A18070306 Previous Articles Next Articles

Special Issue: 有机氟化学

Perspectives

不对称三氟甲硫基化反应研究进展

李树森^a, 王剑波^a,b

a. 北京大学化学与分子工程学院生物有机与分子工程教育部重点实验室北京分子科学国家研究中心北京 100871;
b. 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2018-07-30 发布日期:2018-08-29
通讯作者: 王剑波,E-mail:wangjb@pku.edu.cn E-mail:wangjb@pku.edu.cn
作者简介:李树森,2017年本科毕业于中国科学技术大学.目前在北京大学化学与分子工程学院攻读博士学位.主要从事羰基化合物α位不对称三氟甲基化反应的研究;王剑波,1983年本科毕业于南京理工大学;1990年获日本北海道大学博士学位;1990年至1993年在瑞士日内瓦大学从事博士后研究;1993年至1995年在美国威斯康星大学从事博士后研究;1995年至今在北京大学化学与分子工程学院开展独立研究工作.主要从事过渡金属催化的卡宾转移、卡宾偶联以及基于卡宾的高分子聚合等研究.
基金资助:
项目受国家自然科学基金（No.21332002）和国家重点基础研究发展计划（973计划，No.2015CB856600）资助.

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

Received:2018-07-30 Published:2018-08-29
Contact: 10.6023/A18070306 E-mail:wangjb@pku.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21332002) and the National Basic Research Program of China (973 Program, No. 2015CB856600).

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.

Key words: trifluoromethylthiolation, asymmetric catalysis, organofluorine compounds, stereoselectivity, organic synthesis

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Li Shu-Sen, Wang Jianbo. Recent Advance in Asymmetric Trifluoromethylthiolation[J]. Acta Chim. Sinica, 2018, 76(12): 913-924.

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[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] (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] 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] Bootwicha, T.; Liu, X.; Pluta, R.; Atodiresei, I.; Rueping, M. Angew. Chem., Int. Ed. 2013, 52, 12856.
[5] Wang, X.; Yang, T.; Cheng, X.; Shen, Q. Angew. Chem., Int. Ed. 2013, 52, 12860.
[6] Rueping, M.; Liu, X.; Bootwicha, T.; Pluta, R.; Merkens, C. Chem. Commun. 2014, 50, 2508.
[7] Zhu, X.-L.; Xu, J.-H.; Cheng, D.-J.; Zhao, L.-J.; Liu, X.-Y.; Tan, B. Org. Lett. 2014, 16, 2192.
[8] Yang, T.; Shen, Q.; Lu, L. Chin. J. Chem. 2014, 32, 678.
[9] Liao, K.; Zhou, F.; Yu, J.-S.; Gao, W.-M.; Zhou, J. Chem. Commun. 2015, 51, 16255.
[10] Zhao, B.-L.; Du, D.-M. Org. Lett. 2017, 19, 1036.
[11] Li, M.; Xue, X.-S.; Cheng, J.-P. ACS Catal. 2017, 7, 7977.
[12] Deng, Q.-H.; Rettenmeier, C.; Wadepohl, H.; Gade, L. H. Chem.-Eur. J. 2014, 20, 93.
[13] Jin, M. Y.; Li, J.; Huang, R.; Zhou, Y.; Chung, L. W.; Wang, J. Chem. Commun. 2018, 54, 4581.
[14] Zhang, H.; Leng, X.; Wan, X.; Shen, Q. Org. Chem. Front. 2017, 4, 1051.
[15] Chachignon, H.; Kondrashov, E. V.; Cahard, D. Adv. Synth. Catal. 2018, 360, 965.
[16] Liu, X.; An, R.; Zhang, X.; Luo, J.; Zhao, X. Angew. Chem., Int. Ed. 2016, 55, 5846.
[17] Luo, J.; Liu, Y.; Zhao, X. Org. Lett. 2017, 19, 3434.
[18] Luo, J.; Cao, Q.; Cao, X.; Zhao, X. Nat. Commun. 2018, 9, 527.
[19] Liu, X.; Liang, Y.; Ji, J.; Luo, J.; Zhao, X. J. Am. Chem. Soc. 2018, 140, 4782.
[20] Zhang, Z.; Sheng, Z.; Yu, W.; Wu, G.; Zhang, R.; Chu, W.-D.; Zhang, Y.; Wang, J. Nat. Chem. 2017, 9, 970.
[21] Xu, L.; Wang, H.; Zheng, C.; Zhao, G. Adv. Synth. Catal. 2017, 359, 2942.
[22] Hock, K. J.; Koenigs, R. M. Angew. Chem., Int. Ed. 2017, 56, 13566.
[23] Mao, G.; Chen, L.; Wang, C. Sci. China Chem. 2017, 60, 1565.

不对称三氟甲硫基化反应研究进展

Recent Advance in Asymmetric Trifluoromethylthiolation

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