Synlett 2017; 28(06): 664-668
DOI: 10.1055/s-0036-1588678
letter
© Georg Thieme Verlag Stuttgart · New York

Acid-Catalyzed [3+2] Cycloaddition of Enones with Azomethine Imines for Easy Access to Tetrahydropyrazolopyrazolones

Jovana P. Jovanović
a  Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000 Kragujevac, Serbia   Email: [email protected]
,
Goran A. Bogdanović
b  Vinča Institute of Nuclear Sciences, University of Belgrade, PO Box 522, 11001 Belgrade, Serbia
,
Ivan Damljanović*
a  Faculty of Science, University of Kragujevac, Radoja Domanovića 12, 34000 Kragujevac, Serbia   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 19 August 2016

Accepted after revision: 29 November 2016

Publication Date:
15 December 2016 (online)


Abstract

Aluminum chloride (AlCl3) or zirconium chloride (ZrCl4) catalyzes efficiently the [3+2] cycloaddition of N,N′-cyclic azomethine imines with enones which contain the vinyl group. The scope of the reaction towards various azomethine imines and enones has been explored. Access to diastereomerically pure 6-acyl-5-aryltetrahydropyrazolo[1,2-a]pyrazol-1(5H)-ones is provided by easy chromatographic separations.

Supporting Information

 
  • References and Notes

  • 1 Schumacher JN, Green CR, Best FW, Newell MP. J. Agric. Food Chem. 1977; 25: 310
  • 2 Schatz F, Wagner-Jauregg T. Helv. Chim. Acta 1968; 51: 1919
    • 3a Jungheim LN, Sigmund SK, Fisher JW. Tetrahedron Lett. 1987; 28: 285
    • 3b Ternansky RJ, Draheim SE. Tetrahedron Lett. 1990; 31: 2805
    • 4a Dorn H, Otto A. Angew. Chem., Int. Ed. Engl. 1968; 7: 214
    • 4b Dorn H, Otto A. Chem. Ber. 1968; 101: 3287
  • 5 Shintani R, Fu GC. J. Am. Chem. Soc. 2003; 125: 10778

    • For some selected examples of [3+2] cycloaddition between N,N′-cyclic azomethine imines and compounds that contain a C=C bond, see:
    • 6a Pezdirc L, Jovanovski V, Bevk D, Jakše R, Pirc S, Meden A, Stanovnik B, Svete J. Tetrahedron 2005; 61: 3977
    • 6b Svete J. ARKIVOC 2006; (vii): 35
    • 6c Sibi MP, Rane D, Stanley LM, Soeta T. Org. Lett. 2008; 10: 2971
    • 6d Suga H, Funyu A, Kakehi A. Org. Lett. 2007; 9: 97
    • 6e Li J, Lian X, Liu X, Lin L, Feng X. Chem. Eur. J. 2013; 19: 5134
    • 6f Kato T, Fujinami S, Ukaji Y, Inomata K. Chem. Lett. 2008; 342
    • 6g Ukaji Y, Inomata K. Chem. Rec. 2010; 10: 173
    • 6h Mondal M, Wheeler KA, Kerrigan NJ. Org. Lett. 2016; 18: 4108

      For some selected examples of [3+2] cycloaddition between N,N′-cyclic azomethine imines and compounds that contain a C≡C bond, see:
    • 7a Turk C, Svete J, Stanovnik B, Golič L, Golič-Grdadolnik S, Golobič A, Selič L. Helv. Chim. Acta 2001; 84: 146
    • 7b Pusavec E, Mirnic J, Šenica L, Grošely U, Stanovnik B, Svete J. Z. Naturforsch., B: J. Chem. Sci. 2014; 69: 615
    • 7c Luo N, Zheng Z, Yu Z. Org. Lett. 2011; 13: 3384
    • 7d Arai T, Ogino Y. Molecules 2012; 17: 6170
    • 7e Imaizumi T, Yamashita Y, Kobayashi S. J. Am. Chem. Soc. 2012; 134: 20049
    • 7f Yamashita Y, Kobayashi S. Chem. Eur. J. 2013; 19: 9420
    • 7g Hori M, Sakakura A, Ishihara K. J. Am. Chem. Soc. 2014; 136: 13198

      For some selected examples of [3+2] cycloaddition between N,N′-cyclic azomethine imines and compounds that contain a C=C=C bond, see:
    • 8a Zhou W, Li X.-X, Li G.-H, Wu Y, Chen Z. Chem. Commun. 2013; 49: 3552
    • 8b Jing C, Na R, Wang B, Liu H, Zhang L, Liu J, Wang M, Zhong J, Kwon O, Guo H. Adv. Synth. Catal. 2012; 354: 1023
    • 8c Na R, Jing C, Xu Q, Jiang H, Wu X, Shi J, Zhong J, Wang M, Benitez D, Tkatchouk E, Goddard WA. III, Guo H, Kwon O. J. Am. Chem. Soc. 2011; 133: 13337
    • 8d Na R, Liu H, Li Z, Wang B, Liu J, Wang M.-A, Wang M, Zhong J, Guo H. Tetrahedron 2012; 68: 2349

      For some selected examples of [3+3] cycloaddition of N,N′-cyclic azomethine imines, see:
    • 9a Tong M.-C, Chen X, Tao H.-Y, Wang C.-J. Angew. Chem. Int. Ed. 2013; 52: 12377
    • 9b Guo H, Liu H, Zhu F.-L, Na R, Jiang H, Wu Y, Zhang L, Li Z, Yu H, Wang B, Xiao Y, Hu X.-P, Wang M. Angew. Chem. Int. Ed. 2013; 52: 12641
    • 9c Shintani R, Hayashi T. J. Am. Chem. Soc. 2006; 128: 6330
    • 9d Shapiro ND, Shi Y, Toste FD. J. Am. Chem. Soc. 2009; 131: 11654
    • 9e Xu X, Qian Y, Zavalij PY, Doyle MP. J. Am. Chem. Soc. 2013; 135: 1244
    • 9f Zhu G, Sun W, Wu C, Li G, Hong L, Wang R. Org. Lett. 2013; 15: 4988
    • 9g Li S-N, Yu B, Liu J, Li H-L, Na R. Synlett 2016; 27: 282
  • 10 Xu X, Xu X, Zavalij PY, Doyle MP. Chem. Commun. 2013; 49: 2762
  • 11 Wang L-J, Tang Y In Comprehensive Organic Synthesis . Vol. 4. Knochel P, Molander G.-A. Elsevier; Amsterdam: 2014: 1367
  • 12 Yang D, Fan M, Zhu H, Guo Y, Guo J. Synthesis 2013; 45: 1325
  • 13 General Procedure for [3+2] Cycloaddition of N,N′-Cyclic Azomethine Imines 1 and Enones 2 In a 25 mL flask, enone 2 (0.5 mmol) was added to a stirred mixture of N,N′-cyclic azomethine imine 1 (0.6 mmol) and catalyst (AlCl3 or ZrCl4, 0.1 mmol) in CH2Cl2 (5.0 mL) at r.t. The mixture was stirred for 48 h. The solvent was then removed by distillation, and the crude mixture was separated by silica gel chromatography (hexane–EtOAc = 5:5 to 4:6). Fractions were collected and concentrated in vacuo to provide the pure products 3.
  • 14 Selected Data for Products trans-3a 39% yield for AlCl3-catalyzed reaction (35%yield for ZrCl4-catalyzed reaction), pale yellow solid; mp 90 °C. 1H NMR (200 MHz, CDCl3): δ = 7.50–7.27 (m, 5 H, Ph), 4.13–3.92 (m, 1 H, H-6), 3.74–3.51 (m, 3 H, H-5, H-7a, and H-7b), 3.41 (ddd, J = 11.5, 9.4, 7.6 Hz, 1 H, H-3b), 2.99 (ddd, J = 11.5, 9.0, 6.6 Hz, 1 H, H-3a), 2.84–2.48 (m, 2 H, H-2a, and H-2b), 1.99 (s, 3 H, Me). 13C NMR (50 MHz, CDCl3): δ = 204.1 (CO), 172.9 (C-1), 136.5 (Ph), 128.5 (Ph), 128.2 (Ph), 127.5 (Ph), 70.5 (C-5), 61.7 (C-6), 45.3 (C-3), 42.7 (C-7), 30.7 (C-2), 29.8 (Me). IR (KBr): 3030, 2952, 1713, 1455, 1361, 1169, 750, 703 cm–1. Anal. Calcd for C14H16N2O2 (244.29): C, 68.83; H, 6.60. Found: C, 68.79; H, 6.62. cis-3a 55% yield for AlCl3-catalyzed reaction (54% yield for ZrCl4-catalyzed reaction), white solid; mp 160 °C. 1H NMR (200 MHz, CDCl3): δ = 7.53–7.26 (m, 5 H, Ph), 4.04–3.71 (m, 4 H, H-5, H-6, H-7a, and H-7b), 3.54 (pseudo dt, J = 11.1, 8.2 Hz, 1 H, H-3b), 2.91 (ddd, J = 11.1, 9.5, 6.9 Hz, H-3a), 2.71 (pseudo t, J = 8.2 Hz, 2 H, H-2a, and H-2b), 1.52 (s, 3 H, Me). 13C NMR (50 MHz, CDCl3): δ = 205.4 (CO), 172.3 (C-1), 134.0 (Ph), 128.8 (Ph), 128.6 (Ph), 127.8 (Ph), 71.1 (C-5), 58.0 (C-6), 46.0 (C-3), 42.0 (C-7), 31.6 (C-2), 30.6 (Me). IR (KBr): 3062, 2966, 1709, 1699, 1458, 1357, 1175, 1090, 776, 712 cm–1. Anal. Calcd for C14H16N2O2 (244.29): C, 68.83; H, 6.60. Found: C, 68.80; H, 6.63.
  • 15 CCDC 1497416 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge via www.ccdc.cam.ac.uk/getstructures.
  • 16 In the case of sp2 hybridization, this sum would be equal or close to 360°.