4
Tetrahedron
Rogers, R. S.; Rogier, D. J.; Yu, S. S.; Anderson, G. D.; Burton,
E. G.; Cogburn, J. N.; Gregory, S. A.; Koboldt, C. M.; Perkins, W.
E.; Seibert, K.; Veenhuizen, A. W.; Zhang, Y. Y.; Isakson, P. C. J.
Med. Chem. 1997, 40, 1347.
proceeded smoothly, and the expected product 2a was isolated
in 93% yield (Scheme 6).
Conclusions
3.
(a) Diana, G. D.; Carabateas, P. M.; Williams, G. L.; Pancic, F.;
Steinberg, B. A. J. Med. Chem. 1981, 24, 731; (b) Cocconcelli, G.;
Diodato, E.; Caricasole, A.; Gaviraghi, G.; Genesio, E.; Ghiron,
C.; Magnoni, L.; Pecchioli, E.; Plazzi, P. V.; Terstappen, G. C.
Bioorg. Med. Chem. 2008, 16, 2043; (c) Hassan, S. Y. Molecules
2013, 18, 2683; (d) Ahmad, M.; Aslam, S.; Bukhari, M. H.;
Montero, C.; Detorio, M.; Parvez, M.; Schinazi, R. F. Med. Chem.
Res. 2014, 23, 1309; (e) Aslam, S.; Zaib, S.; Ahmad, M.; Gardiner,
J. M.; Ahmad, A.; Hameed, A.; Furtmann, N.; Gütschow, M.;
Bajorath, J.; Iqbal, J. Eur. J. Med. Chem. 2014, 78, 106; (f) Amin,
K. M.; Abou-Seri, S. M.; Awadallah, F. M.; Eissa, A. A. M.;
Hassan, G. S.; Abdulla, M. M. Eur. J. Med. Chem. 2015, 90, 221.
(a) Cavero, E.; Uriel, S.; Romero, P.; Serrano, J. L.; Giménez, R.
J. Am. Chem. Soc. 2007, 129, 11608; (b) Li, D.; Lv, L.; Sun, P.;
Zhou, W.; Wang, P.; Wu, J.; Kan, Y.; Zhou, H.; Tian, Y. Dyes
Pigm. 2009, 83, 180; (c) Mayoral, M. J.; Ovejero, P.; Campo, J.
A.; Heras, J. V.; Torres, M. R.; Lodeiro, C.; Cano, M. New J.
Chem. 2010, 34, 2766; (d) Manzano, B. R.; Jalón, F. A.; Carrión,
M. C.; Durá, G. Eur. J. Inorg. Chem. DOI:
10.1002/ejic.201501271.
(a) Mahé, O.; Frath, D.; Dez, I.; Marsais, F.; Levacher, V.; Briere,
J.-F. Org. Biomol. Chem. 2009, 7, 3648; (b) Fustero, S.; Sánchez-
Roselló, M.; Barrio, P.; Simón-Fuentes, A. Chem. Rev. 2011, 111,
6984; (c) Janin, Y. L. Chem. Rev. 2012, 112, 3924; (d) Zhang, G.;
Ni, H.; Chen, W.; Shao, J.; Liu, H.; Chen, B.; Yu, Y. Org. Lett.
2013, 15, 5967; (e) Chen, B.; Zhu, C.; Tang, Y.; Ma, S. Chem.
Commun. 2014, 50, 7677; (f) Hu, X.-Q.; Chen, J.-R.; Wei, Q.; Liu,
F.-L.; Deng, Q.-H.; Beauchemin, A. M.; Xiao, W.-J. Angew.
Chem. Int. Ed. 2014, 53, 12163; (g) Shao, N.; Chen, T.; Zhang, T.;
Zhu, H.; Zheng, Q.; Zou, H. Tetrahedron 2014, 70, 795; (h)
Mantenuto, S.; Mantellini, F.; Favi, G.; Attanasi, O. A. Org. Lett.
2015, 17, 2014; (i) Pérez-Aguilar, M. C.; Valdés, C. Angew.
Chem. Int. Ed. 2015, 54, 13729; (j) Vanjari, R.; Guntreddi, T.;
Kumar, S.; Singh, K. N. Chem. Commun. 2015, 51, 366; (k)
Comas-Barceló, J.; Blanco-Ania, D.; Broek, S. A. M. W.;
Nieuwland, P. J.; Harrity, J. P. A.; Rutjes, F. P. J. T. Catal. Sci.
Technol. DOI: 10.1039/c5cy02247a.
(a) Hayter, M. J.; Bray, D. J.; Clegg, J. K.; Lindoy, L. F. Synth.
Commun. 2006, 36, 707; (b) Sanchez-Carmona, M. A.; Contreras-
Cruz, D. A.; Miranda, L. D. Org. Biomol. Chem. 2011, 9, 6506; (c)
Kumari, K.; Raghuvanshi, D. S.; Jouikov, V.; Singh, K. N.
Tetrahedron Lett. 2012, 53, 1130.
(a) Willy, B.; Müller, T. J. J. Eur. J. Org. Chem. 2008, 4157; (b)
Zhang, Z.; Tan, Y.-J.; Wang, C.-S.; Wu, H.-H. Heterocycles 2014,
89, 103; (c) Zhang, X.; Kang, J.; Niu, P.; Wu, J.; Yu, W.; Chang,
J. J. Org. Chem. 2014, 79, 10170.
(a) Pinto, D. C. G. A.; Silva, A. M. S.; Almeida, L. M. P. M.;
Cavaleiro, J. A. S.; Elguero, J. Eur. J. Org. Chem. 2002, 3807; (b)
Sviridov, S. I.; Vasil’ev, A. A.; Shorshnev, S. V. Tetrahedron
2007, 63, 12195.
Sanders, D. C.; Marczak, A.; Melendez, J. L.; Shechter, H. J. Org.
Chem. 1987, 52, 5622.
In summary, a simple, green and practical system for the
regioselective preparation of 1H-pyrazole derivatives in the
presence of 2 mol% iodine using TsNHNH2 as nitrogen-transfer
reagent in EtOH under mild conditions has been demonstrated. In
contrast with reported procedures, the present procedure is
applicable and highly efficient, and has the advantage of short
reaction time and high yields. Moreover, the utilization of
catalytic amounts of iodine as an efficient catalyst to synthesize
pyrazole moiety in a one-pot condensation and cyclization
manner has been testified to be reliable. Last but not the least, the
present transformation proceeds in good yields and
commendably tolerates a wide range of functional groups, which
paves the way for the synthesis of 1H-pyrazoles and will gain
much attention in multidisciplinary fields for the preparation of
potentially bioactive derivatives.
4.
5.
Acknowledgments
We thank the National Natural Science Foundation of China
(No.21542007), the Program for New Century Excellent Talents
in University (NCET-11-0053), the Fundamental Research Funds
of the Central Universities (DUT15TD25) for support of this
work.
References and notes
1.
(a) Catalan, J.; Fabero, F.; Claramunt, R. M.; Maria, M. D. S.;
Foces-Foces, M. C.; Cano, F. H.; Martinez-Ripoll, M.; Elguero, J.;
Sastre, R. J. Am. Chem. Soc. 1992, 114, 5039; (b) Shen, W. C.;
Wang, Y. J.; Cheng, K. L.; Lee, G. H.; Lai, C. K. Tetrahedron
2006, 62, 8035; (c) Schmidt, A.; Dreger, A. Curr. Org. Chem.
2011, 15, 2897; (d) Schmidt, A.; Guan, Z. Synthesis 2012, 44,
3251; (e) Schnatterer, S. Phenylpyrazole-Containing Fiprole
Insecticides, in Bioactive Heterocyclic Compound Classes:
Agrochemicals; Lamberth, C., Ed.; Wiley-VCH: Weinheim,
Germany, 2012; (f) Giornala, F.; Pazenok, S.; Rodefeld, L.; Lui,
N.; Vors, J.-P.; Leroux, F. R. J. Fluorine Chem. 2013, 152, 2; (g)
Kumar, V.; Kaur, K.; Gupta, G. K.; Sharma, A. K. Eur. J. Med.
Chem. 2013, 69, 735; (h) Kasiotis, K. M.; Tzanetou, E. N.;
Haroutounian, S. A. Front. Chem. 2014, 2, 78; (i) Pérez-
Fernández, R.; Goya, P.; Elguero, J. Arkivoc. 2014, 2014, 233; (j)
Li, C.; Liang, L.; Wang, K.; Bian, C.; Zhang, J.; Zhou, Z. J.
Mater. Chem. A 2014, 2, 18097; (k) Lipunova, G. N.; Nosova, E.
V.; Charushin, V. N.; Chupakhin, O. N. J. Fluorine Chem. 2015,
175, 84; (l) Li, W.; Li, J.; Wang, F.; Gao, Z.; Zhang, S. ACS Appl.
Mater. Interfaces 2015, 7, 26206; (m) Küçükgüzel, G.; Şenkardeş,
S. Eur. J. Med. Chem. 2015, 97, 786; (n) Rai, S. K.; Srivastava, P.;
Gupta, H.; Puerta, M. del C.; Valerga, P.; Tewari, A. K. Struct.
Chem. 2015, 26, 555; (o) Dutter, B. F.; Mike, L. A.; Reid, P. R.;
Chong, K. M.; Ramos-Hunter, S. J.; Skaar,E. P.; Sulikowski, G. A.
ACS Chem. Biol. DOI: 10.1021/acschembio.5b00934.
6.
7.
8.
9.
10. Wen, J.; Fu, Y.; Zhang, R.-Y.; Zhang, J.; Chen, S.-Y.; Yu, X.-Q.
Tetrahedron 2011, 67, 9618.
11. (a) Chen, Z.; Yan, Q.; Liu, Z.; Zhang, Y. Chem. Eur. J. 2014, 20,
17635; (b) Wei, W.; Wen, J.; Yang, D.; Guo, M.; Wang, Y.; You,
J.; Wang, H. Chem. Commun. 2015, 51, 768; (c) Wang, F.-X.;
Tian, S.-K. J. Org. Chem. 2015, 80, 12697; (d) Zhu, Y.-L.; Jiang,
B.; Hao, W.-J.; Qiu, J.-K.; Sun, J.; Wang, D.-C.; Wei, P.; Wang,
A.-F.; Li, G.; Tu, S.-J. Org. Lett. 2015, 17, 6078; (e) Wang, S.;
Huang, X.; Wang, Q.; Ge, Z.; Wang, X.; Li, R. RSC Adv. 2016, 6,
11754.
12. Gao, W.-C.; Jiang, S.; Wang, R.-L.; Zhang, C. Chem. Commun.
2013, 49, 4890.
13. Compound 2t was purified by column chromatography on neutral
Al2O3.
2.
(a) De Wald, H. A.; Lobbestael, S.; Poschel, B. P. H. J. Med.
Chem. 1981, 24, 982; (b) Vinge, E.; Bjorkman, S. B. Acta
Pharmacol. Toxicol. 1986, 59, 165; (c) Hosie, A. M.; Baylis, H.
A.; Buckingham, S. D.; Sattelle, D. B. Br. J. Pharmacol. 1995,
115, 909; (d) Terrett, N. K.; Bell, A. S.; Brown, D.; Ellis, P.
Bioorg. Med. Chem. Lett. 1996, 6, 1819; (e) Penning, T. D.;
Talley, J. J.; Bertenshaw, S. R.; Carter, J. S.; Collins, P. W.;
Docter, S.; Graneto, M. J.; Lee, L. F.; Malecha, J. W.; Miyashiro,
J.
M.;