Citation: Liu Xunshen, Li Meimei, You Jun, Liu Bo. Asymmetric 1, 3-Dipolar Cycloaddition Reaction of C, N-Diarylnitrone with N-α, β-Unsaturated Acylpyrazoles Catalyzed by Ni-DBFOX/Ph[J]. Chinese Journal of Organic Chemistry, ;2017, 37(1): 86-91. doi: 10.6023/cjoc201608019 shu

Asymmetric 1, 3-Dipolar Cycloaddition Reaction of C, N-Diarylnitrone with N-α, β-Unsaturated Acylpyrazoles Catalyzed by Ni-DBFOX/Ph

Liu Xunshen ,
Li Meimei ,
You Jun ^*,, ,
Liu Bo ^*,,

Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040

Corresponding author: You Jun, Liu Bo,
Received Date: 23 August 2016
Revised Date: 13 September 2016

Fund Project: the National Natural Science Foundation of China 21506043the Innovative Research Team Foundation of Green Chemical Technology in the University of Heilongjiang Province 2014TD007

Figures(1)

Using (R, R)-4, 6-dibenzofurandiyl-2, 2'-bis (4-phenyloxazoline)-Ni (Ni-DBFOX) as the catalyst, asymmetric catalytic 3-dipolar cycloaddition reactions between N-α, β-unsaturated acylpyrazoles and C, N-diarylnitrone have been developed with 95% regioselectivity and an endo/exo ratio of 99:1 with >90% ee of the endo-diastereomer.Influence of olefins, nitrone structure, metal type and amount of catalyst on the reaction stereoselectivity was also carefully discussed.
- asymmetric catalysis,
- 1, 3-dipolar cycloaddition,
- DBFOX/Ph,
- C, N-diarylnitrone,
- N-α, β-unsaturated acylpyrazoles,
- enantioselectivity
1. [1]
  Gothelf, K.-V.; Jørgensen, K.-A.; Benito, A. Chem. Rev. 1998, 98, 863. doi: 10.1021/cr970324e
2. [2]
  Padwa, A.; Pearson, W.-H. Synthetic Applications of 1, 3-Dipolar Cycloaddition Chemistry toward Heterocycles and Natural Products, John Wiley and Sons, Hoboken, NJ, 2003, pp. 818~899.
3. [3]
  Stanley, L.-M.; Sibi, M.-P. Chem. Rev.2008, 108, 2887. doi: 10.1021/cr078371m
4. [4]
  Karanjule, N.-S.; Markad, S.-D.; Sharma, T.; Sabharwal, S.-G.; Pu-ranik, V.-G.; Dhavale, D.-D. J. Org. Chem. 2005, 70, 1356. doi: 10.1021/jo048176x
5. [5]
  Chiacchio, U.; Corsaro, A.; Iannazzo, D.; Piperno, A.; Pistarà, V.; Rescifina, A.; Romeo, R.; Valveri, V.; Mastino, A.; Romeo, G. J. Med. Chem. 2003, 46, 3696. doi: 10.1021/jm0308186
6. [6]
  Houk, K.-N.; Sims, J.; Watts, C.-R.; Luskus, L.-J. J. Am. Chem. Soc. 1973, 31, 7903.
7. [7]
  Gothelf, K.-V.; Hazell, R.-G.; Jørgensen, R.-G. J. Org. Chem. 1996, 61, 346. doi: 10.1021/jo951204e
8. [8]
  Kagan, H.-B.; Riant, O. Chem. Rev. 1992, 92, 1007. doi: 10.1021/cr00013a013
9. [9]
  Seiji, I.; Yosuke, I.; Herman, S.-W.; Aoki, K.; Nishiyama, H. Tetra-hedron Lett. 2004, 45, 2121. doi: 10.1016/j.tetlet.2004.01.043
10. [10]
  You, J.; Liu, L.-X.; Liu, B.; Yu, Y.-C. J. Chem. Res. 2012, 36, 131. doi: 10.3184/174751912X13303666057373
11. [11]
  Banerjee, B.; Capps, S.-G.; Kang, J.; Robinson, J.-W.; Castle, S.-L. J. Org. Chem. 2008, 73, 8973. doi: 10.1021/jo801721z
12. [12]
  (a) Kanemasa, S.; Oderaotoshi, Y.; Tanaka, J.; Wada, E. J. Am. Chem. Soc. 1998, 120, 12355.
  (b) Kanemasa, S.; Oderaotoshi, Y.; Sakaguchi, S.; Yamamoto, H.; Tanaka, J.; Wada, E.; Curran, D.-P. J. Am. Chem. Soc. 1998, 120, 3074.
13. [13]
  Sakaguchi, Y.; Kurono, N.; Yamauchi, K. Org. Lett. 2014, 16, 808. doi: 10.1021/ol403545b
14. [14]
  Sakakura, A.; Hori, M.; Fushimi, M.; Ishihara, K. J. Am. Chem. Soc. 2010, 132, 15550. doi: 10.1021/ja1081603
15. [15]
  Hashimoto, Y.; Itoh, K.; Kakehi, A.; Shiro, M.; Suga, H. J. Org. Chem. 2013, 78, 6182. doi: 10.1021/jo400858u
16. [16]
  Kashima, C.; Takahashi, K.; Fukuchi, I.; Fukusaka, K. Heterocycles 1997, 44, 289. doi: 10.3987/COM-96-S19
17. [17]
  Sibi, M.; Soeta, T. J. Am. Chem. Soc. 2007, 129, 4522. doi: 10.1021/ja069312d
18. [18]
  Zheng, Y.-Q.; Yao, Y.-Q.; Ye, L. Tetrahedron.2016, 72, 973. doi: 10.1016/j.tet.2015.12.067
19. [19]
  Zhang, J.-L.; Liu, X.-H.; Wang, R. Chem.-Eur. J.2014, 20, 4911. doi: 10.1002/chem.201304835
20. [20]
  Shen, X.-D.; Huo, H.-H.; Wang, C.-Y. Chem.-Eur. J. 2015, 21, 9720. doi: 10.1002/chem.201500922
21. [21]
  Sibi, M.; Itoh, K. J. Am. Chem. Soc. 2007, 129, 8064. doi: 10.1021/ja071739c
22. [22]
  Dong, X.-Q.; Fang, X.; Tao, H.-Y. Chem. Commun. 2012, 48, 7238. doi: 10.1039/c2cc31891a
23. [23]
  Tyson, E.-L.; Farney, E.-P.; Yoon, T.-P. Org.Lett. 2012, 14, 1110. doi: 10.1021/ol3000298
24. [24]
  Jensen, K.-B.; Gothelf, K.-V.; Jørgensen, K.-V. Helv. Chim. Acta 1997, 80, 2039. doi: 10.1002/hlca.v80:7
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