Synthesis of α-onoceradiene-like terpene dimers by intermolecular metathesis processes

Organic Letters

Volumn 8, Issue 4, 2006, Pages 593-596

  De La Torre, María C ^a   Deometrio, Antonio M ^a   Álvaro, Elsa ^a   García, Isabel ^a   Sierra, Miguel A ^b  

^a INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

^b UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

DITERPENE; SCLAREOLIDE; TERPENE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

CATALYSIS; DITERPENES; MOLECULAR STRUCTURE; STEREOISOMERISM; TERPENES;

EID: 33644753725     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol052680m     Document Type: Article

References (34)

1. Comprehensive Natural Products Chemistry; Barton, D., Nakanishi, K., Meth-Cohn, O., Eds.; Pergamon: Elsevier 1999.
2. (a) Tietze, L. F.; Bell, H. P.; Chandrasekhar, S. Angew. Chem., Int. Ed. 2003, 42, 3996.
3. (b) Mehta, G.; Singh, V. Chem. Soc. Rev. 2002, 31, 324.
4. (a) For an overview of this field, see: Dagani, R. Chem. Eng. News 2002, 80, 23.
5. (b) See also the special issue on bioorganometallic chemistry: J. Organomet. Chem. 1999, 589 (1).
6. (a) Sierra, M. A.; de la Torre, M. C. Angew. Chem., Int. Ed. 2000, 39, 1538.
7. (b) Sierra, M. A.; de la Torre M. C. Dead Ends and Detours: Direct ways to Successful Total Synthesis; Wiley-VCH: New York, 2004.
8. Clemons, P. A. Curr. Opin. Chem. Biol. 1999, 3, 112.
9. Diver, S. T.; Schreiber, S. L. J. Am. Chem. Soc. 1997, 119, 5106 and references therein.
10. Nicolaou, K. C.; Hughes, R.; Cho, S.-Y.; Winssinger, N.; Smethurst, C.; Labischinski, H.; Endermann, R. Angew. Chem., Int. Ed. 2000, 39, 3823 and references therein.
11. (a) Mackay, J. P.; Gerhard, U.; Beauregard, D. A.; Maplestone, R. A.; Williams, D. H. J. Am. Chem. Soc. 1994, 116, 4573.
12. (b) Loll, P. J.; Bevivino, A. E.; Korty, B. D.; Axelen, P. H. J. Am. Chem. Soc. 1997, 119, 1516.
13. (c) Beauregard, D. A.; Williams, D. H., Gwynn, M. N.; Knowles, D. J. C. Antimicrob. Agents Chemoter. 1994, 116, 781.
14. Li, Y.; Dias, J. R. Chem. Rev. 1997, 97, 283.
15. (a) de la Torre, M. C.; García, I.; Sierra, M. A. Chem. Eur. J. 2005, 11, 3659.
16. (b) Alvaro, E.; de la Torre, M. C.; Sierra, M. A. Org. Lett. 2003, 5, 2381.
17. See, for instance: Yan, J.; Zhang, X.-M.; Li, Z.-R.; Zhou, L.; Chen, J.-Ch.; Sun, L.-R.; Qiu, M.-H- Helv. Chim. Acta 2005, 88, 240 and references therein.
18. Jacob, J.; Disnar, J.-R.; Boussafir, M.; Ledru, M. P.; Albuquerque, A. L. S.; Sifeddine, A.; Turcq, B. Org. Geochem. 2004, 35, 289.
19. β-Onocerine and β-onoceradiene have been recently synthesized by Barrero and co-workers; see: Barrera, A. F.; Herrador, M. M.; Quílez del Moral, J. F.; Arteaga, P.; Arteaga, J. F.; Piedra, M.; Sánchez, E. M. Org. Lett. 2005, 7, 2301.
20. (+)-α-Onocerin has been synthesized by Corey and co-workers; see: Mi, Y.; Schreiber, J. V.; Corey, E. J. J. Am. Chem. Soc. 2002, 124, 11290.
21. Orhan, I.; Terzioglu, S.; Sener, B. Planta Med. 2003, 69, 265.
22. Despite the explosive growth of the use of metathesis in organic and organometallic chemistry, its use in the preparation of homodimers derived from natural products has been restricted to a synthesis of a FK506 dimer (FK1012); see ref 6. While this manuscript was being prepared, the synthesis of new artemisinin-derived dimers by self-cross-metathesis was reported; see: Grellepois, F.; Crousse, B.; Bonnet-Delpon, D.; Bégué, J. P. Org. Lett. 2005, 7, 5219.
23. (a) de la Torre, M. C.; García, I.; Sierra, M. A. J. Nat. Prod. 2002, 65, 661.
24. (b) de la Torre, M. C.; García, I.; Sierra, M. A. Tetrahedron Lett. 2002, 43, 6351.
25. (c) de la Torre, M. C.; García, I.; Sierra, M. A. J. Org. Chem. 2003, 68, 6611.
26. The drimane sesquiterpenoid systematic numbering has been adopted for the decalin framework of the compounds synthesized in this paper. See: Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman and Hall: London, 1991; Vol. 1.
27. 2: C. 83.02; H, 10.84. Found: C, 82.93; H, 10.81.
28. 1H NMR.
29. Breitmaier, E.; Voelter, W. Carbon-13 NMR Spectroscopy. High-Resolution Methods and Applications in Organic Chemistry and Biochemistry; VCH: New York, 1987; pp 192-195.
30. The γ,δ- to α,β-unsaturated ketone isomerization (3b to 6) may be due to the active participation of Grubbs' catalyst in the hydride transfer. However, this process requires the addition of alcohols and bases to the reaction mixture. See: Schmidt, B. Chem. Commun. 2004, 742 and the pertinent references therein. In our case, the increased yield of 6 in toluene pointed to an uncatalyzed thermal isomerization rather to the participation of Grubbs' catalyst.
31. Fráter, G.; Helmlinger, D.; Kraft, P. Helv. Chim. Acta 2003, 86, 678.
32. 36FeO: C, 75.67; H, 8.16. Found: C, 75.73; H, 8.10.
33. Regioisomeric derivatives were also detected in the crude reaction mixture.
34. It should be noted that ferrocenyl derivatives 11 and 9 are labdane organometallic hybrids.