基于氟烷基自由基过程构建手性中心的研究进展

doi:10.6023/cjoc201808030

有机化学 ›› 2019, Vol. 39 ›› Issue (1): 1-14.DOI: 10.6023/cjoc201808030 上一篇下一篇

所属专题：庆祝陈庆云院士九十华诞

综述与进展

基于氟烷基自由基过程构建手性中心的研究进展

黄航^a, 王兮^a, 王剑波^b

a 湖南大学化学化工学院长沙 410082;
b 北京大学化学与分子工程学院北京 100871

收稿日期:2018-08-27 修回日期:2018-11-21 发布日期:2018-11-30
通讯作者: 王兮, 王剑波 E-mail:cccewangxi@hnu.edu.cn;wangjb@pku.edu.cn
基金资助:
国家自然科学基金（No.21332002）资助项目.

Research Developments of the Construction of Chiral Center Based on Fluoroalkyl Radical Reactions

Huang Hang^a, Wang Xi^a, Wang Jianbo^b

a College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082;
b College of Chemistry and Molecular Engineering, Peking University, Beijing 100871

Received:2018-08-27 Revised:2018-11-21 Published:2018-11-30
Contact: 10.6023/cjoc201808030 E-mail:cccewangxi@hnu.edu.cn;wangjb@pku.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21332002).

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摘要/Abstract

含氟的有机化合物被广泛地应用于制药、农业化学品、材料科学等多个领域.三氟甲基、二氟甲基、全氟烷基等是应用非常广泛的含氟官能团，因此发展普适高效的引入氟烷基的新方法具有重大意义.氟烷基自由基反应近年来已经发展成为引入氟烷基的有效方法.另一方面，氟烷基取代的手性有机分子的合成也受到了人们的重点关注.然而由于氟烷基自由基的高反应活性，其反应的选择性较难控制，特别是关于对映选择性控制的报道不多，更缺乏相关综述予以总结.综述了近二十年来基于氟烷基自由基过程的不对称合成方法的研究进展，对各反应的选择性、普适性、反应机理等方面进行着重介绍.本综述根据反应机理分为三部分：（1）经由氟烷基自由基的烯醇/烯胺中间体不对称氟烷基化；（2）经由氟烷基自由基的烯烃不对称双官能团化；（3）经由氟烷基自由基的烯基硼酸酯酸根型复合物立体选择性1，2-迁移.

关键词: 氟烷基化, 自由基, 不对称合成, 催化

Fluorine-containing organic compounds have been widely applied in various fields, such as pharmacy, agrochemicals, materials science, etc. Trifluoromethyl, difluoromethyl and perfluoroalkyl groups represent the typical fluorine-containing functional groups. Hence, the development of highly efficient methods for introducing fluoroalkyl groups is of primary importance. In recent years, the reactions based on fluoroalkyl radicals have been developed into competent methods for introducing fluoroalkyl groups. On the other hand, the synthesis of the chiral molecules containing fluoroalkyl groups has attracted considerable attentions. However, attributed to the high reactivity of the fluoroalkyl radicals, the control of the reaction selectivity is difficult. Particularly, so far there have been only limited reports on the enantiocontrol of the reaction in this regard and the corresponding review of the field still lacks. This review summarizes the research on the asymmetric synthesis based on fluoroalkyl radical reactions developed over the past 20 years. The review introduces the selectivities, scope and mechanism of various reactions. It is divided into three different parts according to the type of the reaction: (1) asymmetric fluoroalkylation of enol/enamine intermediate through fluoroalkyl radical, (2) asymmetric difunctionalization of olefin through fluoroalkyl radical, (3) stereoselective 1,2-shift of vinylboronate complexes through fluoroalkyl radical.

Key words: fluoroalkylation, radicals, asymmetric synthesis, catalysis References

引用此文

黄航, 王兮, 王剑波. 基于氟烷基自由基过程构建手性中心的研究进展[J]. 有机化学, 2019, 39(1): 1-14.

Huang Hang, Wang Xi, Wang Jianbo. Research Developments of the Construction of Chiral Center Based on Fluoroalkyl Radical Reactions[J]. Chin. J. Org. Chem., 2019, 39(1): 1-14.

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参考文献

[1] (a) Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470.
(b) Shimizu, M.; Hiyama, T. Angew. Chem., Int. Ed. 2005, 44, 214.
[2] Lehmann, F. Arch. Exp. Pathol. Pharmakol. 1928, 130, 250.
[3] Kirsch, P. Modern Fluoroorganic Chemistry, Synthesis, Reactivity, Applications, Wiley-VCH, Weinheim, 2004.
[4] (a) Ma, J.-A.; Cahard, D. Chem. Rev. 2004, 104, 6119.
(b) Ma, J.-A.; Cahard, D. Chem. Rev. 2008, 108, PR1.
(c) Nie, J.; Guo, H.-C.; Cahard, D.; Ma, J.-A. Chem. Rev. 2011, 111, 455.
[5] Dolbier, W. R. Chem. Rev. 1996, 96, 1557.
[6] (a) Studer, A. Angew. Chem., Int. Ed. 2012, 51, 8950.
(b) Wang, X.; Zhang, Y.; Wang, J. Sci. Sin. 2012, 42, 1417.
[7] Pan, X.; Xia, H.; Wu, J. Org. Chem. Front. 2016, 3, 1163.
[8] Wang, F.; Chen, P.; Liu, G. Acc. Chem. Res. 2018, 51, 2036.
[9] (a) Fessenden, R. W.; Schuler, R. H. J. Chem. Phys. 1965, 43, 2704.
(b) Krusic, P. J.; Bingham, R. C. J. Am. Chem. Soc. 1976, 98, 230.
[10] (a) Wang, S.-M.; Han, J.-B.; Zhang, C.-P.; Qin, H.-L.; Xiao, J.-C. Tetrahedron 2015, 71, 7949.
(b) Chatterjee, T.; Iqbal, N.; You, Y.; Cho, E. J. Acc. Chem. Res. 2016, 49, 2284.
(c) Wang, X.; Studer, A. Acc. Chem. Res. 2017, 50, 1712.
(d) Barata-Vallejo, S.; Cooke, M. V.; Postigo, A. ACS Catal. 2018, 8, 7287.
[11] (a) Iseki, K.; Nagai, T.; Kobayashi, Y. Tetrahedron Lett. 1993, 34, 2169.
(b) Iseki, K.; Nagai, T.; Kobayashi, Y. Tetrahedron:Asymmetry 1994, 5, 961.
[12] Itoh, Y.; Mikami, K. Tetrahedron 2006, 62, 7199.
[13] Nagib, D. A.; Scott, M. E.; MacMillan, D. W. C. J. Am. Chem. Soc. 2009, 131, 10875.
[14] Wozniak, L.; Murphy, J. J.; Melchiorre, P. J. Am. Chem. Soc. 2015, 137, 5678.
[15] Herrmann, A. T.; Smith, L. L.; Zakarian, A. J. Am. Chem. Soc. 2012, 134, 6976.
[16] Huo, H.; Huang, X.; Shen, X.; Harmsa, K.; Meggers, E. Synlett 2016, 27, 749.
[17] Liu, J.; Ding, W.; Zhou, Q.-Q.; Liu, D.; Lu, L.-Q.; Xiao, W.-J. Org. Lett. 2018, 20, 461.
[18] Yajima, T.; Nagano, H. Org. Lett. 2007, 9, 2513.
[19] Zhu, R.; Buchwald, S. L. Angew. Chem., Int. Ed. 2013, 52, 12655.
[20] Miller, Y.; Miao, L.; Hosseini, A. S.; Chemler, S. R. J. Am. Chem. Soc. 2012, 134, 12149.
[21] Wang, F.; Wang, D.; Wan, X.; Wu, L.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2016, 138, 15547.
[22] Wu, L.; Wang, F.; Wan, X.; Wang, D.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2017, 139, 2904.
[23] Fu, L.; Zhou, S.; Wan, X.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2018, 140, 10965.
[24] Yu, P.; Lin, J.-S.; Li, L.; Zheng, S.-C.; Xiong, Y.-P.; Zhao, L.-J.; Tan, B.; Liu, X.-Y. Angew. Chem., Int. Ed. 2014, 53, 11890.
[25] Li, T.; Yu, P.; Du, Y.-M.; Lin, J.-S.; Zhi, Y.; Liu, X.-Y. J. Fluorine Chem. 2017, 203, 210.
[26] Lin, J.-S.; Dong, X.-Y.; Li, T.-T.; Jiang, N.-C.; Tan, B.; Liu, X.-Y. J. Am. Chem. Soc. 2016, 138, 9357.
[27] Lin, J.-S.; Wang, F.-L.; Dong, X.-Y.; He, W.-W.; Yuan, Y.; Chen, S.; Liu, X.-Y. Nat. Commun. 2017, 8, 14841.
[28] Cheng, Y.-F.; Dong, X.-Y.; Gu, Q.-S.; Yu, Z.-L.; Liu X.-Y. Angew. Chem., Int. Ed. 2017, 56, 8883.
[29] Li, X.-T.; Gu, Q.-S.; Dong, X.-Y.; Meng, X.; Liu, X.-Y. Angew. Chem., Int. Ed. 2018, 57, 7668.
[30] Kischkewitz, M.; Okamoto, K.; Mück-Lichtenfeld, C.; Studer, A. Science 2017, 355, 936.
[31] Gerleve, C.; Kischkewitz, M.; Studer, A. Angew. Chem., Int. Ed. 2018, 57, 2441.

基于氟烷基自由基过程构建手性中心的研究进展

Research Developments of the Construction of Chiral Center Based on Fluoroalkyl Radical Reactions

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