Chemical Papers

, Volume 67, Issue 1, pp 59–65 | Cite as

Thiophenium-ylides: Synthesis and reactivity

  • Aleš Machara
  • Jiří SvobodaEmail author
Original Paper


The reaction of propanedioic acid, 2-diazo-1,3-bis(1,1-dimethylethyl) ester (di-tert-butyl diazomalonate) with a series of cyclopenta[b]thiophenes in the presence of catalytic rhodium acetate was studied. The resulting S—C ylides underwent a rearrangement to form a heterocycle with different topology; thialene, in very low yields. Experimental and spectral data for all compounds are provided.


cyclopenta[b]thiophene thiophenium-ylide rhodium catalysis thialene 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Bonini, B. F., Capito, E., Comes-Franchini, M., Ricci, A., Bottoni, A., Bernardi, F., Miscione, G. P., Giordano, L., & Cowley, A. R. (2004). Diastereoselective synthesis of thieno[3′,2′:4,5]cyclopenta[1,2-d][1,3]oxazolines t new ligands fot the copper-catalyzed asymmetric conjugate addition of diethylzinc to enones. European Journal of Organic Chemistry, 2004, 4442–4451. DOI: 10.1002/ejoc.200400351.CrossRefGoogle Scholar
  2. Bowles, T., Jones, R., Porter, A. E. A., Rechka, J. A., Rzepa, H. S., & Williams, D. J. (1985). 2H-thiopyrans as intermediates in the rearrangement of thiophenium bisalkoycarbonylmethylides to thiophene-2-malonates; the crystal and molecular structure of 2,2-bis-t-butoxycarbonyl-5-bromo-2Hthiopyran and 2,2-bis-t-butoxycarbonyl-6-bromo-2H-thiopyran. Journal of the Chemical Society, Chemical Communications, 1985, 1590–1592. DOI: 10.1039/c39850001590.CrossRefGoogle Scholar
  3. Bowles, T., Gillespie, R. J., Porter, A. E. A., Rechka, J. A., & Rzepa, H. S. (1988a). Thermally induced rearrangement of thiopheniobis(alkoxycarbonyl)methanides. Journal of the Chemical Society, Perkin Transactions 1, 1988, 803–807. DOI: 10.1039/p19880000803.CrossRefGoogle Scholar
  4. Bowles, T., Jones, R., Porter, A. E. A., Rechka, J. A., Rzepa, H. S., & Williams, D. J. (1988b). Synthesis of some thiophenium bis(t-butoxycarbonyl)methylides. Journal of the Chemical Society, Perkin Transactions 1, 1988, 1023–1027. DOI: 10.1039/p19880001023.CrossRefGoogle Scholar
  5. Ito, Y., Borecka, B., Olovsson, G., Trotter, J., & Scheffer, J. R. (1995). Control of the solid-state photodimerization of some derivatives and analogs of trans-cinnamic acid by ethylenediamine. Tetrahedron Letters, 36, 6087–6090. DOI: 10.1016/0040-4039(95)01210-9.CrossRefGoogle Scholar
  6. Klein, R. F. X., & Horák, V. (1986). New synthesis and spectroscopic studies of thialene (cyclopenta[b]thiapyran). Journal of Organic Chemistry, 51, 4644–4651. DOI: 10.1021/jo00374a027.CrossRefGoogle Scholar
  7. Mayer, R., Franke, J., Horák, V., Hanker, I., & ZahradnÍk, V. (1961). Synthese und Eigenschaften des Thialens (Cyclopenta-Thiapyran). Tetrahedron Letters, 2, 289–294. DOI: 10.1016/s0040-4039(01)84064-8.CrossRefGoogle Scholar
  8. Mayer, R., & Franke, J. (1965). Schwefel-Helerocyclen. XLII. Eine weitere Synthese von Thialen (Cyclopenta[b]thiopyran) und die erste Darstellung des Benzothialens Indeno[2,1-b] thiopyran. Journal für Praktische Chemie, 30, 262–272. DOI: 10.1002/prac.19650300505.CrossRefGoogle Scholar
  9. Machara, A., Kurfürst, M., KozmÍk, V., Petříčková H., Dvořáková, H., & Svoboda, J. (2004). A nonconcerted cycloaddition of fused 2-vinylthiophenes with dimethyl acetylenedicarboxylate. Tetrahedron Letters, 45, 2189–2192 DOI: 10.1016/j.tetlet.2004.01.030.CrossRefGoogle Scholar
  10. Machara, A., KozmÍk, V., Pojarová, M., Dvořáková, H., & Svoboda, J. (2009). Preparation and rearrangement study of novel thiophenium- and selenophenium-ylides. Collection of Czechoslovak Chemical Communications, 74, 785–798. DOI: 10.1135/cccc2009001.Google Scholar
  11. MacKenzie, N. E., & Thomson, R. H. (1982). Ring contractions of thiochroman-4-ones and thiochromen-4-ones. Journal of the Chemical Society, Perkin Transactions 1, 1982, 395–402. DOI: 10.1039/p19820000395.CrossRefGoogle Scholar
  12. Mohamadi, F., Spees, M. M., & Grindey, G. B. (1992). Sulfonylureas: a new class of cancer chemotherapeutic agents. Journal of Medicinal Chemistry, 35, 3012–3016. DOI: 10.1021/jm00094a013.CrossRefGoogle Scholar
  13. Poirier, Y., & Lozach, N. (1966). Heterocyclic sulfur-compounds. XXII. Sulfuration of 2-alkylidene-1-indanones and 2-arylmethylene-1-indanones. Bulletin de la Societe Chimique de France, 1966, 1062–1068.Google Scholar
  14. Porter, A. E. A. (1989). The chemistry of thiophenium salts and thiophenium ylids. Advances in Heterocyclic Chemistry, 45, 151–184. DOI: 10.1016/s0065-2725(08)60330-x.CrossRefGoogle Scholar
  15. Sam, J., & Thompson, A. C. (1963). Thiaindanones. Thiophene isosteres of indanone. Journal of Pharmaceutical Sciences, 52, 898–901. DOI: 10.1002/jps.2600520918.CrossRefGoogle Scholar
  16. Smith, D. G. (1990). 4-Amido-3,4-dihydro-2H-1-benzothiopyran-3-ols and their sulphoxide and sulphone derivatives — cromakalim analogues. Journal of the Chemical Society, Perkin Transactions 1, 1990, 3187–3191. DOI: 10.1039/p19900003187.CrossRefGoogle Scholar
  17. Stuckwisch, C. G., & Bailey, J. V. (1963). Reaction of organometallic compounds with propiolactone. The Journal of Organic Chemistry, 28, 2362–2363. DOI: 10.1021/jo01044a050.CrossRefGoogle Scholar
  18. Vuorinen, E., Chalmers, A. A., Dillen, J. L. M., & Modro, T. A. (1991). Benzo[b]thiophenium S,C-ylides: Preparation, structure and comparison with thiophenium analogues. Tetrahedron, 47, 8611–8620. DOI: 10.1016/s0040-4020(01)82404-2.CrossRefGoogle Scholar
  19. Yuen, P.W. (2004). U.S. Patent No. 6710190 Washington, D.C., USA: U.S. Patent and Trademark Office.Google Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2012

Authors and Affiliations

  1. 1.Department of Organic ChemistryInstitute of Chemical TechnologyPrague 6Czech Republic

Personalised recommendations