Citation: Xing Li, Zhi-Qin Sun, Hong-Hong Chang, Wen-Long Wei. Highly efficient regioselective ring openings of N-tosylaziridines to haloamines using ferric (Ⅲ) halides[J]. Chinese Chemical Letters, ;2014, 25(8): 1174-1178. doi: 10.1016/j.cclet.2014.03.033 shu

Highly efficient regioselective ring openings of N-tosylaziridines to haloamines using ferric (Ⅲ) halides

1.
Department of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Corresponding author: Wen-Long Wei,
Received Date: 11 December 2013
Available Online: 26 February 2014
Fund Project: We appreciate gratefully the Natural Science Foundation of Shanxi Province (Nos. 2012021007-2, 2011011010-2) for financial support. The project is also supported by Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (No. 20120006). (Nos. 2012021007-2, 2011011010-2)

FeX₃ (X=Cl, Br) were found to be very effective reagents and powerful catalysts for regioselective ring openings of a variety of N-tosylaziridines with them to afford the corresponding β-haloamines in good to excellent yields with high regioselectivity under mild conditions. At the same time, 13 new compounds were obtained firstly. Moreover, the β-bromoamine prepared could be transferred into β-nitroamine with NaNO₂ in moderate yield.
- Ring-opening,
- N-Tosylaziridine,
- Haloamine,
- Ferric (Ⅲ) halide,
- Regioselectivity
1. [1]
  [1] P.F. Lu, Recent developments in regioselective ring opening of aziridines, Tetrahedron 66 (2010) 2549-2560.
2. [2]
  [2] G.S. Singh, M. D'hooghe, N. De Kimpe, Synthesis and reactivity of C-heteroatomsubstituted aziridines, Chem. Rev. 107 (2007) 2080-2135.
3. [3]
  [3] I.D.G. Watson, L. Yu, A.K. Yudin, Advances in nitrogen transfer reactions involving aziridines, Acc. Chem. Res. 39 (2006) 194-206.
4. [4]
  [4] X.E. Hu, Nucleophilic ring opening of aziridines, Tetrahedron 60 (2004) 2701-2743.
5. [5]
  [5] J.B. Sweeney, Aziridines: epoxides' ugly cousins? Chem. Soc. Rev. 31 (2002) 247-258.
6. [6]
  [6] W. McCoull, F.A. Davis, Recent synthetic applications of chiral aziridines, Synthesis (2000) 1347-1365.
7. [7]
  [7] P. Dauban, R.H. Dodd, 2,3-Aziridino-2,3-dideoxy-D-ribono-g-lactone 5-phosphonate: stereocontrolled synthesis from D-lyxose and unusual aziridine ring opening, J. Org. Chem. 62 (1997) 4277-4284.
8. [8]
  [8] G. Chouhan, H. Alper, Domino ring-opening/carboxamidation reactions of N-tosyl aziridines and 2-halophenols/pyridinol: efficient synthesis of 1,4-benzo-and pyrido-oxazepinones, Org. Lett. 12 (2010) 192-195.
9. [9]
  [9] G.D. Sala, A. Lattanzi, Highly enantioselective synthesis of β-amidophenylthioethers by organocatalytic desymmetrization of meso-aziridines, Org. Lett. 11 (2009) 3330-3333.
10. [10]
  [10] E. Leemans, S. Mangelinckx, N. De Kimpe, Novel synthesis of chiral unactivated 2-aryl-1-benzylaziridines, Synlett (2009) 1265-1268.
11. [11]
  [11] B. Crousse, S. Narizuka, D. Bonnet-Delpon, J.P. Bengue, First stereoselective synthesis of cis 3-CF₃-aziridine-2-carboxylates. A route to new (trifluoromethyl) α-functionalised β-amino acids, Synlett (2001) 679-681.
12. [12]
  [12] C.A. Ray, E. Risberg, P. Somfai, Lewis acid-catalyzed hetero Diels-Alder cycloadditions of 3-alkyl, 3-phenyl and 3-carboxylated 2H-azirines, Tetrahedron Lett. 42 (2001) 9289-9291.
13. [13]
  [13] D. Gnecco, F.L. Orea, A. Galindo, et al., Regiospecific and enantiospecific ring opening of methyl (+)-(1'R, 2R)-and (-)-(1'R, 2S)-1-(2-phenylethanol) aziridine-2-carboxylates, Molecules 5 (2000) 998-1003.
14. [14]
  [14] M.K. Ghorai, K. Das, A. Kumar, K. Ghosh, An efficient route to regioselective opening of N-tosylaziridines with zinc(Ⅱ) halides, Tetrahedron Lett. 46 (2005) 4103-4106.
15. [15]
  [15] G. Righi, T. Franchini, C. Bonini, Highly regioselective opening of optically active N-Boc-2,3-aziridino alcohol derivatives with metal halides, Tetrahedron Lett. 39 (1998) 2385-2388.
16. [16]
  [16] C. Bonini, G. Righi, R. D'Achille, Regioselective opening of 3-substituted N-ethoxycarbonyl aziridine-2-carboxylates with metal halides toward the preparation of α and β-amino acids, Tetrahedron Lett. 37 (1996) 6893-6896.
17. [17]
  [17] G. Sabitha, R.S. Babu, M. Rajkumar, C.S. Reddy, J.S. Yadav, Highly regioselective ring opening of epoxides and aziridines using cerium(Ⅲ) chloride, Tetrahedron Lett. 42 (2001) 3955-3958.
18. [18]
  [18] J.S. Yadav, B.V.S. Reddy, G.M. Kumar, Indium trihalide mediated regioselective ring opening of aziridines: a facile synthesis of 2-haloamines, Synlett (2001) 1417-1418.
19. [19]
  [19] G. Righi, C. Potini, P. Bovicelli, Stereo-and regioselective ring opening of alkenyl aziridines with metal halides, Tetrahedron Lett. 43 (2002) 5867-5869.
20. [20]
  [20] C.H. Ding, L.X. Dai, X.L. Hou, An efficient and highly regioselective fluorination of aziridines using BF₃·OEt₂ as fluorine source, Synlett (2004) 2218-2220.
21. [21]
  [21] J. Wu, X.Y. Sun, W. Sun, S.Q. Ye, Unexpected highly efficient ring-opening of aziridines or epoxides with iodine promoted by thiophenol, Synlett (2006) 2489-2491.
22. [22]
  [22] B. Das, M. Krishnaiah, K. Venkateswarlu, Regio-and stereoselective ring opening of epoxides and aziridines using zirconyl chloride: an efficient approach for the synthesis of β-chlorohydrins and β-chloroamines, Chem. Lett. 36 (2007) 82-83.
23. [23]
  [23] M. Kumar, S.K. Pandey, S. Gandhi, V.K. Singh, PPh₃/halogenating agent-mediated highly efficient ring opening of activated and non-activated aziridines, Tetrahedron Lett. 50 (2009) 363-365.
24. [24]
  [24] M. Narender, K. Surendra, N.S. Krishnaveni, M.S. Reddy, K.R. Rao, A facile regioselective ring opening of aziridines to haloamines using tetrabutylammoniumhalides in the presence ofb-cyclodextrin in water, Tetrahedron Lett. 45 (2004) 7995-7997.
25. [25]
  [25] M.K. Pandey, A. Bisai, V.K. Singh, Regioselective ring opening of aziridines with activated DMF complexes: a facile synthesis of β-haloamines, Tetrahedron Lett. 45 (2004) 9661-9663.
26. [26]
  [26] M.K. Ghorai, A. Kumar, D.P. Tiwari, BF₃·OEt₂-Mediated highly regioselective SN₂-type ring-opening of N-activated aziridines and N-activated azetidines by tetraalkylammonium halides, J. Org. Chem. 75 (2010) 137-151.
27. [27]
  [27] Q.J. Li, M. Shi, C. Timmons, G.G. Li, FeCl₃-Catalyzed aminohalogenation of arylmethylenecyclopropanes and arylvinylidenecyclopropanes and corresponding mechanistic studies, Org. Lett. 8 (2006) 625-628.
28. [28]
  [28] C. Bolm, J. Legros, J.L. Paih, L. Zani, Iron-Catalyzed reactions in organic synthesis, Chem. Rev. 104 (2004) 6217-6254.
29. [29]
  [29] (a) D. Kano, S. Minakata, M. Komatsu, Novel organic-solvent-free aziridination of olefins: chloramine-T-I2 system under phase-transfer catalysis conditions, J. Chem. Soc. Perkin Trans. 1 (2001) 3186-3188; (b) V.V. Thakur, A. Sudalai, N-Bromoamides as versatile catalysts for aziridination of olefins using chloramine-T, Tetrahedron Lett. 44 (2003) 989-992.
1. [1]
  Qiuyun Li , Yannan Zhu , Yining Wang , Gang Qi , Wen-Juan Hao , Kelu Yan , Bo Jiang . Catalytic CH activation-initiated transdiannulation: An oxygen transfer route to ring-fluorinated tricyclic γ-lactones. Chinese Chemical Letters, 2024, 35(9): 109494-. doi: 10.1016/j.cclet.2024.109494
2. [2]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
3. [3]
  Rong-Nan Yi , Wei-Min He . Visible light/copper catalysis enabled radial type ring-opening of sulfonium salts. Chinese Chemical Letters, 2025, 36(4): 110787-. doi: 10.1016/j.cclet.2024.110787
4. [4]
  Qinghong Zhang , Qiao Zhao , Xiaodi Wu , Li Wang , Kairui Shen , Yuchen Hua , Cheng Gao , Yu Zhang , Mei Peng , Kai Zhao . Visible-light-induced ring-opening cross-coupling of cycloalcohols with vinylazaarenes and enones via β-C-C scission enabled by proton-coupled electron transfer. Chinese Chemical Letters, 2025, 36(2): 110167-. doi: 10.1016/j.cclet.2024.110167
5. [5]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
6. [6]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
7. [7]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
8. [8]
  Peiyan Zhu , Yanyan Yang , Hui Li , Jinhua Wang , Shiqing Li . Rh(Ⅲ)‐Catalyzed sequential ring‐retentive/‐opening [4 + 2] annulations of 2H‐imidazoles towards full‐color emissive imidazo[5,1‐a]isoquinolinium salts and AIE‐active non‐symmetric 1,1′‐biisoquinolines. Chinese Chemical Letters, 2024, 35(10): 109533-. doi: 10.1016/j.cclet.2024.109533
9. [9]
  Yinghui Xia , Yixi Lin , Zhenming Xu . Cation potential guiding structural regulation of lithium halide superionic conductors. Chinese Journal of Structural Chemistry, 2025, 44(3): 100448-100448. doi: 10.1016/j.cjsc.2024.100448
10. [10]
  Shu-Ran Xu , Fang-Xing Xiao . Metal halide perovskites quantum dots: Synthesis, and modification strategies for solar CO2 conversion. Chinese Journal of Structural Chemistry, 2023, 42(12): 100173-100173. doi: 10.1016/j.cjsc.2023.100173
11. [11]
  Pan Liu , Yanming Sun , Alberto J. Fernández-Carrión , Bowen Zhang , Hui Fu , Lunhua He , Xing Ming , Congling Yin , Xiaojun Kuang . Bismuth-based halide double perovskite Cs₂KBiCl₆: Disorder and luminescence. Chinese Chemical Letters, 2024, 35(5): 108641-. doi: 10.1016/j.cclet.2023.108641
12. [12]
  Xiuwen Xu , Quan Zhou , Yacong Wang , Yunjie He , Qiang Wang , Yuan Wang , Bing Chen . Expanding the toolbox of metal-free organic halide perovskite for X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109272-. doi: 10.1016/j.cclet.2023.109272
13. [13]
  Jiajing Wu , Ru-Ling Tang , Sheng-Ping Guo . Three types of promising functional building units for designing metal halide nonlinear optical crystals. Chinese Journal of Structural Chemistry, 2024, 43(6): 100291-100291. doi: 10.1016/j.cjsc.2024.100291
14. [14]
  Huan Hu , Ying Zhang , Shi-Shuang Huang , Zhi-Gang Li , Yungui Liu , Rui Feng , Wei Li . Temperature- and pressure-responsive photoluminescence in a 1D hybrid lead halide. Chinese Journal of Structural Chemistry, 2024, 43(10): 100395-100395. doi: 10.1016/j.cjsc.2024.100395
15. [15]
  Jiayuan Liang , Xin Mi , Songhao Guo , Hui Luo , Kejun Bu , Tonghuan Fu , Menglin Duan , Yang Wang , Qingyang Hu , Rengen Xiong , Peng Qin , Fuqiang Huang , Xujie Lü . Pressure-induced emission in 0D metal halide (EATMP)SbBr5 by regulating exciton-phonon coupling. Chinese Journal of Structural Chemistry, 2024, 43(7): 100333-100333. doi: 10.1016/j.cjsc.2024.100333
16. [16]
  Han Yan , Jingming Yao , Zhangran Ye , Qiaoquan Lin , Ziqi Zhang , Shulin Li , Dawei Song , Zhenyu Wang , Chuang Yu , Long Zhang . Al-F co-doping towards enhanced electrolyte-electrodes interface properties for halide and sulfide solid electrolytes. Chinese Chemical Letters, 2025, 36(1): 109568-. doi: 10.1016/j.cclet.2024.109568
17. [17]
  Zhenzhen Zhao , Meichen Jiao , Jiejie Ling , Han Jiang , Yan Gao , Hao Xu , Hai-Qing Li , Jingang Jiang , Peng Wu , Le Xu . Toward the microporous zeolite family with tunable large-medium cage and pore opening. Chinese Journal of Structural Chemistry, 2024, 43(9): 100336-100336. doi: 10.1016/j.cjsc.2024.100336
18. [18]
  Wenling Yuan , Fengli Li , Zhe Chen , Qiaoxin Xu , Zhenhua Guan , Nanyu Yao , Zhengxi Hu , Junjun Liu , Yuan Zhou , Ying Ye , Yonghui Zhang . AbnI: An α-ketoglutarate-dependent dioxygenase involved in brassicicene CH functionalization and ring system rearrangement. Chinese Chemical Letters, 2024, 35(5): 108788-. doi: 10.1016/j.cclet.2023.108788
19. [19]
  Jing-Qi Tao , Shuai Liu , Tian-Yu Zhang , Hong Xin , Xu Yang , Xin-Hua Duan , Li-Na Guo . Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade. Chinese Chemical Letters, 2024, 35(6): 109263-. doi: 10.1016/j.cclet.2023.109263
20. [20]
  Wenyu Gao , Liming Zhang , Chuang Zhao , Lixiang Liu , Xingran Yang , Jinbo Zhao . Controlled semi-Pinacol rearrangement on a strained ring: Efficient access to multi-substituted cyclopropanes by group migration strategy. Chinese Chemical Letters, 2024, 35(9): 109447-. doi: 10.1016/j.cclet.2023.109447

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(717)
HTML views(2)

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