Skip to main content
Log in

Green chemistry approaches to the regioselective synthesis of spiro heterobicyclic rings using iodine as a new and efficient catalyst under solvent-free conditions

  • Short Communication
  • Published:
Molecular Diversity Aims and scope Submit manuscript

Abstract

Iodine catalyzes the pseudo four-component reaction of an aldehyde, a urea or thiourea, and cyclic 1,3-dicarbonyl compounds under microwave irradiation in a solvent-free condition to yield various σ symmetric spiro heterobicyclic rings in excellent yields.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

References

  1. Biginelli P (1893) Synthesis of tetrahydropyrimidinones by the acid catalyzed condensation of an aldehyde, a β-ketoester and urea. Gazz Chim Ital 23: 360–416

    Google Scholar 

  2. Yarim M, Sarac S, Kilic FS, Erol K (2003) Synthesis and in vitro calcium antagonist activity of 4-aryl-7,7-dimethyls1,7, 7,-trimethyl-1,2,3,4,5,6,7,8-octahydroquinazoline-2,5-dione derivatives. Il Farmaco 58: 17–24. doi:10.1016/S0014-827X(02)00009-5

    Article  PubMed  CAS  Google Scholar 

  3. Byk G, Gettlieb HE, Herscovici J, Mirkin F (2000) New regioselective multicomponent reaction: One pot synthesis of spiro heterocyclic aliphatic rings. J Comb Chem 2: 732–735. doi:10.1021/cc000056p

    Article  PubMed  CAS  Google Scholar 

  4. Mokrosz JL, Paluchowska MH, Szneler E, Drozdz B (1989) The effect of aryl substituents in some spiro[2-oxo-4,6-bis(aryl)hexahydropyrimidine-5,5′-barbituric acids]. Arch Chem (Weinheim, Germany) 322: 231–235

    Article  CAS  Google Scholar 

  5. Mamaev VP, Borovik VP (1968) Spiro[2-oxo-4,6-bis(aryl)hexahydropyrimidine-5,5′-barbituric acids]. Izobret Prom Obraztsy Tovarnye Znaki 45:24; Chem Absrt 69: 96790f

  6. Borovik VP, Mamaev VP (1970) Synthesis of sulfur-containing spiropyrimidine barbituric acids. Kim Farm Zh 4:32–35; Chem Abstr 72:111411

    Google Scholar 

  7. Abelman MM, Smith SC, James DR (2003) Cyclic ketones and substituted α-keto acids as alternative substrates for novel Biginelli-like scaffold synthesis. Tetrahedron Lett 44: 4559–4562. doi:10.1016/S0040-4039(03)00985-7

    Article  CAS  Google Scholar 

  8. Field KW, Wilder D, Utz A, Kolb KE (1987) Addition of Iodine to alkenes: A pseudo first-, second-, or third-order kinetics experiment. J Chem Educ 64: 269–270. doi:10.1021/ed064p269

    Article  CAS  Google Scholar 

  9. Klein J (1959) The Iodolactonization of Cyclohexaneacetic Acids. J Am Chem Soc 81: 3611–3614. doi:10.1021/ja01523a035

    Article  CAS  Google Scholar 

  10. Freiberg LA (1967) Mechanism of oxidation of enolizable nonmethyl ketones by base and iodine. The role of atmospheric oxygen. J Am Chem Soc 89: 5297–5298. doi:10.1021ja00996a045

    Article  CAS  Google Scholar 

  11. Kirk KC (1978) Facile synthesis of 2-substituted imidazoles. J Org Chem 43: 4381–4383. doi:10.1021jo00416a033

    Article  CAS  Google Scholar 

  12. Brown HC, Rathke MW, Rogic MM, DeLue NR (1988) Organoboranes for synthesis. 9. Rapid reaction of organoboranes with iodine under the influence of base. A convenient procedure for the conversion of alkenes into iodides via hydroboration. Tetrahedron 44: 2751–2762. doi:10.1016/S0040-4020(88)90010-5

    CAS  Google Scholar 

  13. Zweifel G, Fisher RP, Snow JT, Whitney CC (1972) Convenient synthesis of trans olefins from alkynes via hydroboration-cyanohalogenation. J Am Chem Soc 94: 6560–6561. doi:10.1021/ja00773a059

    Article  CAS  Google Scholar 

  14. Shaabani A, Bazagir A (2004) Microwave-assisted efficient synthesis of spiro-fused heterocycles under solvent-free conditions. Tetrahedron Lett 45: 2575–2577. doi:j.tetlet.2004.01.154

    Article  CAS  Google Scholar 

  15. Santagada V, Frecentese F, Perissutti E, Favretto L, Caliendo G (2004) The application of microwaves in combinatorial and high-throughput synthesis as new synthetic procedure in drug discovery. QSAR Comb Sci 23: 919–944. doi:10.1002/qsar.200420039

    Article  CAS  Google Scholar 

  16. Choudhary VR, Tillu VH, Narkhede VS, Borate HB, Wakhardar RD (2003) Microwave assisted solvent-free synthesis of dihydropyrimidinones by Biginelli reaction over Si-MCM-41 supported FeCl3 catalyst. Cat Commun 4: 449–453. doi:10.1016/S1566-7367(03)/00111-0

    Article  CAS  Google Scholar 

  17. Kuhnert N (2002) Microwave-assisted reactions in organic synthesis—Are there any nonthermal microwave effects?. Angew Chem Int Edn 41: 1863–1866. doi:10.1002/1521-3773(20020603)41:11<1863

    Article  CAS  Google Scholar 

  18. Manufactured by M/s Prolabo, 54 rue Roger Salengro; F-94126 Fontenay-Sous-Bois, Cedix-France, Tel: 01 45 14 85 00; Fax: 01 45 14 85 15; Fax Export: 33 145148616

  19. Kappe CO (1997) A reexamination of the mechanism of the Biginelli dihydropyrimidine synthesis. Support for an N-acyliminium ion intermediate. J Org Chem 62: 7201–7204. doi:10.1021/jo971010u

    Article  PubMed  CAS  Google Scholar 

  20. Folkers K, Johnson TB (1933) Researches on pyrimidines. CXXXVI. The mechanism of formation of tetrahydropyrimidines by the Biginelli reaction. J Am Chem Soc 55: 3784–3791. doi:10.1021/ja01336a053

    Article  CAS  Google Scholar 

  21. Kaup G, Reza Naim MJ, Schmeyers J (2003) Sovent free Knoevenagel condensation and Michael additions in the solid state and in the melt with quantitative yield. Tetrahedron 59: 3753–3760. doi:10.1016/S0040-4020(03)00554-4

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Dipak Prajapati.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Prajapati, D., Bhuyan, D., Gohain, M. et al. Green chemistry approaches to the regioselective synthesis of spiro heterobicyclic rings using iodine as a new and efficient catalyst under solvent-free conditions. Mol Divers 15, 257–261 (2011). https://doi.org/10.1007/s11030-010-9247-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11030-010-9247-4

Keywords

Navigation