Synthesis 2020; 52(09): 1379-1386
DOI: 10.1055/s-0039-1691591
paper
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Tandem Dehydrocyanation and [3+2] Cyclo­addition Reactions of Phenacylmalononitriles: Regioselective Synthesis of Functionalized 4-Benzoyl-5-cyanopyrazoles under Mild Conditions

Issa Yavari
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Email: yavarisa@modares.ac.ir
,
Omid Khaledian
› Author Affiliations
We are grateful to the Research Council of Tarbiat Modares University for support of this work.
Further Information

Publication History

Received: 14 November 2019

Accepted after revision: 14 January 2020

Publication Date:
06 February 2020 (online)


Abstract

A novel copper-catalyzed [3+2] cycloaddition reaction with concomitant in situ generation of benzoylacrylonitriles and nitrile imines from phenacylmalononitriles and hydrazonoyl chlorides, respectively, is reported. The reaction was performed using copper(I) chloride as catalyst and N-methylimidazole as a clean complexing agent/weak base to afford the functionalized 4-benzoyl-5-cyanopyrazoles in moderate to good yields and excellent regioselectivity under ambient conditions. This method provides rapid access to a wide range of highly functionalized 4-benzoyl-5-cyanopyrazoles.

Supporting Information

 
  • References

    • 1a Bekhit AA, Saudi MN, Hassan AM, Fahmy SM, Ibrahim TM, Ghareeb D, El-Seidy AM, Nasralla SN, Bekhit AE.-D. A. Eur. J. Med. Chem. 2019; 163: 353
    • 1b Burgart YV, Agafonova N, Shchegolkov E, Borisevich S, Khursan S, Maslova V, Triandafilova G, Solodnikov SY, Krasnykh O, Saloutin V. J. Fluorine Chem. 2019; 218: 1
    • 1c Khan I, Sirisha K, Shareef MA, Ganapathi T, Shaik AB, Kunta CS, Kamal A, Kumar CG. Chem. Biol. Drug Des. 2019; 94: 1339
    • 1d Mohamed LW, Shaaban MA, Zaher AF, Alhamaky SM, Elsahar AM. Bioorg. Chem. 2019; 83: 47
    • 1e Abdellatif KR, Fadaly WA, Kamel GM, Elshaier YA, El-Magd MA. Bioorg. Chem. 2019; 82: 86
  • 2 Singer RA, Caron S, McDermott RE, Arpin P, Do NM. Synthesis 2003; 1727
  • 3 Singh P, Paul K, Holzer W. Bioorg. Med. Chem. 2006; 14: 5061
    • 4a Dai T, Li Q, Zhang X, Yang C. J. Org. Chem. 2019; 84: 5913
    • 4b Koca I, Özgür A, Coşkun KA, Tutar Y. Bioorg. Med. Chem. 2013; 21: 3859
    • 4c Riyadh SM, Farghaly TA, Abdallah MA, Abdalla MM, Abd El-Aziz MR. Eur. J. Med. Chem. 2010; 45: 1042

      See for example:
    • 5a Kikugawa H, Nagayama S, Sano M. (Ishihara Sangyo Kaisha Ltd) US Patent 8,435,928, 2013
    • 5b Shimoharada H, Tsukamoto M, Ikeguchi M, Kikugawa H, Sano M, Kitahara Y, Kominami H, Okita T. (Ishihara Sangyo Kaisha Ltd) US Patent 8,030,498, 2011
  • 6 Carey F, Giuliano R. Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group. In Organic Chemistry, 8th ed. McGraw-Hill; New York: 2011: 724
    • 7a Crocetti L, Schepetkin IA, Cilibrizzi A, Graziano A, Vergelli C, Giomi D, Khlebnikov AI, Quinn MT, Giovannoni MP. J. Med. Chem. 2013; 56: 6259
    • 7b Mizuhara T, Kato T, Hirai A, Kurihara H, Shimada Y, Taniguchi M, Maeta H, Togami H, Shimura K, Matsuoka M. Bioorg. Med. Chem. Lett. 2013; 23: 4557
    • 8a Caboni P, Sammelson RE, Casida JE. J. Agric. Food Chem. 2003; 51: 7055
    • 8b Sammelson RE, Caboni P, Durkin KA, Casida JE. Bioorg. Med. Chem. 2004; 12: 3345
  • 9 Elie R, Rüther E, Farr I, Emilien G, Salinas E. J. Clin. Psychiatry 1999; 60: 536
  • 10 Johnson TW, Richardson PF, Bailey S, Brooun A, Burke BJ, Collins MR, Cui JJ, Deal JG, Deng Y.-L, Dinh D. J. Med. Chem. 2014; 57: 4720
    • 11a Das B, Reddy CR, Kumar DN, Krishnaiah M, Narender R. Synlett 2010; 391
    • 11b Finholt A, Jacobson E, Ogard A, Thompson P. J. Am. Chem. Soc. 1955; 77: 4163
    • 11c Swain CG. J. Am. Chem. Soc. 1947; 69: 2306
    • 11d Huisgen R, Grashey R, Seidel M, Wallbillich G, Knupfer H, Schmidt R. Justus Liebigs Ann. Chem. 1962; 653: 105
  • 12 Huisgen R. Angew. Chem., Int. Ed. Engl. 1963; 2: 565
    • 13a Sibi MP, Stanley LM, Jasperse CP. J. Am. Chem. Soc. 2005; 127: 8276
    • 13b Sibi MP, Stanley LM, Soeta T. Adv. Synth. Catal. 2006; 348: 2371
    • 13c Wang G, Liu X, Huang T, Kuang Y, Lin L, Feng X. Org. Lett. 2012; 15: 76
    • 13d Gerten AL, Slade MC, Pugh KM, Stanley LM. Org. Biomol. Chem. 2013; 11: 7834
  • 14 Voronin VV, Ledovskaya MS, Gordeev EG, Rodygin KS, Ananikov VP. J. Org. Chem. 2018; 83: 3819
    • 15a Liu Y, Nappi M, Escudero-Adán EC, Melchiorre P. Org. Lett. 2012; 14: 1310
    • 15b Nesmeyanov AN, Rybinskaya MI. Dokl. Akad. Nauk SSSR 1958; 120: 793

      See, for example:
    • 16a Raulet C. Bull. Soc. Chim. Fr. 1974; 531
    • 16b Motoki S, Satsumabayashi S, Masuda T. Bull. Chem. Soc. Jpn. 1966; 39: 1519
    • 16c Nudelman A, Keinan E. Synthesis 1982; 687
    • 16d Trabulsi H, Guillot R, Rousseau G. Eur. J. Org. Chem. 2010; 5884
    • 16e Runcie KA, Taylor RJ. Chem. Commun. 2002; 974
  • 17 Hauser CR, Brasen WR. J. Am. Chem. Soc. 1956; 78: 82
  • 18 Bachon A.-K, Opatz T. J. Org. Chem. 2016; 81: 1858
    • 19a Yavari I, Khalili G. Synlett 2010; 1862
    • 19b Yavari I, Khalili G, Mirzaei A. Helv. Chim. Acta 2010; 93: 277
    • 19c Yavari I, Nematpour M, Sodagar E. Monatsh. Chem. 2015; 146: 2135
    • 19d Yavari I, Nematpour M, Yavari S, Sadeghizadeh F. Tetrahedron Lett. 2012; 53: 1889
    • 19e Yavari I, Taheri Z, Naeimabadi M, Bahemmat S, Halvagar MR. Synlett 2018; 29: 918
  • 20 Abdelhamid AO, Negm AM, Abbas IM. J. Prakt. Chem. 1989; 331: 31
  • 21 Zhang CY, Liu XH, Wang BL, Wang SH, Li ZM. Chem. Biol. Drug Des. 2010; 75: 489
  • 22 Garve LK, Petzold M, Jones PG, Werz DB. Org. Lett. 2016; 18: 564
  • 23 Shawali AS, Párkanyi C. J. Heterocycl. Chem. 1980; 17: 833
  • 24 CCDC 1965090 (3k) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
  • 25 Dadiboyena S. Eur. J. Med. Chem. 2013; 63: 347
  • 26 Alishetty S, Shih H.-P, Han C.-C. Org. Lett. 2018; 20: 2513