Short Report

 

Short Synthesis of a New Cyclopentene-1,3-dione Derivative Isolated from Piper carniconnectivum

 

Luiz C. Dias*, Simone B. Shimokomaki and Robson T. Shiota

 

Instituto de Química, Universidade Estadual de Campinas, CP 6154, 13083-970 Campinas - SP, Brazil. * e-mail: ldias@iqm.unicamp.br

 

Received: September 20, 2004
Published on the web: March 30, 2005

 

Abstract

The total synthesis of cyclopentene-1,3-dione (1), a new natural cyclopentenedione derivative isolated from the roots of Piper carniconnectivum, is described in 8 steps and 11% overall yield from 2-acetylfuran, giving a 57:43 mixture of the two possible geometric isomers 1a and 1b.

Keywords: aldol reaction, allylic alcohol oxidation, cyclopentenedione derivative, Piper carniconnectivum

 

Resumo

А síntese total da ciclopentenodiona (1), isolada das raízes de Piper carniconnectivum, é descrita em 8 etapas e 11% de rendimento global a partir do 2-acetilfurano, fornecendo uma mistura 57:43 dos dois possíveis isômeros geométricos 1a e 1b.

 

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References

1. Facundo, V. A.; Sá , A. L.; Silva, S. A. F.; Morais, S. M.; Matos, C. R. R.; Braz-Filho, R.; J. Braz.. Chem. Soc. 2004, 15, 140.         [ Links ]

2. Ribeiro, J. E. L. da S.; Hopkins, M. J. G.; Vincentin, A.; Sothers, C. A.; Costa, M. A. da S.; de Brito, J. M.; de Souza, M. A. D.; Martins, L. H. P.; Lohmann, L. G.; Assunção, P. A. C. L.; Pereira, E. da C.; Mesquita, M. R.; Procópio, L. C.; Flora da Reserva Ducke - Guia de Identificação das Plantas Vasculares de uma Floresta de Terra-Firme na Amazônia Central, INPA-DFID: Manaus, Amazonas, Brasil, 1999. p. 181.         [ Links ]

3. For other compounds isolated from the Piper genus, see: Parmar, V. S.; Jain, S. C.; Bisht, K. S.; Jain, R.; Taneja, P.; Jha, A.; Tyagi, O. D.; Prasad, A. K.; Wengel, J.; Olsen, C. E.; Boll, P. M.; Phytochemistry 1997, 46, 597.         [ Links ]

4. The numbering of (1) as well as of each intermediate follows that suggested in reference 1.

5. West, F. G.; Gunawardena, G. U.; J. Org. Chem. 1993, 58, 2402.         [ Links ] Furylcarbinol (5) could also be obtained by the reaction of 2-lithium furan with acetaldehyde in 84% yield.

6. Piancatelli, G.; Scettri, A.; David, G.; D'Auria, M.; Tetrahedron 1978, 34, 2775;         [ Links ] West, F. G.; Gunawardena, G. U.; J. Org. Chem. 1993, 58, 5043;         [ Links ] Piancatelli, G.; D'Auria, M.; D'Onofrio, F.; Synthesis 1994, 867.         [ Links ]

7. Scettri, A.; Piancatelli, G.; D'Auria, M.; David, G.; Tetrahedron 1979, 35, 135;         [ Links ] Shono, T.; Hamaguchi, H.; Aoki, K.; Chem. Lett. 1977, 1053;         [ Links ] Csáky, A. G.; Mba, M.; Plumet, J.; J. Org. Chem. 2001, 66, 9026;         [ Links ] Csáky, A. G.; Mba, M.; Plumet, J.; Synlett 2003, 2092.         [ Links ]

8. Corey, E. J.; Gilman, N. W.; Ganem, B. E.; J. Am. Chem. Soc. 1968, 90, 5616.         [ Links ]

9. For large scale preparations of cyclopentenedione 12, the use of Jones oxidation conditions is recommended. See: Lola, D.; Belakovs, S.; Gavars, M.; Turovskis, I.; Kemme, A.; Tetrahedron 1998, 54, 1589.         [ Links ]

10. Olivieri, A. C.; González-Sierra, M.; Rúveda, E.; A.; J. Org. Chem. 1986, 51, 2824.         [ Links ]

11. Mancuso, A. J.; Swern, D.; Synthesis 1981, 165.         [ Links ]

12. New compounds and the additional isolated intermediates gave satisfactory ¹H and ¹³C NMR, IR, HRMS and analytical data. Yields refer to chromatographically and spectroscopically homogeneous materials.

 

Notes

Dedicated to Prof. Raimundo Braz-Filho for his outstanding contributions to the field of Organic Chemistry in Brazil.