Short total syntheses of both the putative and actual structures of the clerodane diterpenoid (±)-sacacarin by double annulation

Organic Letters

Volumn 3, Issue 25, 2001, Pages 4027-4030

  Grossman, Robert B ^a   Rasne, Ravindra M ^a  

^a UNIVERSITY OF KENTUCKY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DITERPENE; FURAN DERIVATIVE; PLANT EXTRACT; SACACARIN;

ARTICLE; BARK; CHEMICAL STRUCTURE; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS; TRADITIONAL MEDICINE;

DITERPENES; FURANS; MAGNETIC RESONANCE SPECTROSCOPY; MEDICINE, TRADITIONAL; MOLECULAR STRUCTURE; PLANT BARK; PLANT EXTRACTS; SUPPORT, NON-U.S. GOV'T; SUPPORT, U.S. GOV'T, NON-P.H.S.; SUPPORT, U.S. GOV'T, P.H.S.;

EID: 0035856894     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016748j     Document Type: Article

References (26)

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2. Merritt, A. T.; Ley, S. V. Nat. Prod. Rep. 1992, 243. Rodríguez-Hahn, L.; Esquivel, B.; Cárdenas, J. In Progress in the Chemistry of Organic Natural Products; Herz, W., Kirby, G. W., Moore, R. E., Steglich, W., Tamm, C., Eds.; Springer-Verlag: New York, 1994; Vol. 63, p 107. Piozzi, F. Heterocycles 1994, 37, 603. Piozzi, F.; Bruno, M.; Rosselli, S. Heterocycles 1998, 48, 2185.
3. Merritt, A. T.; Ley, S. V. Nat. Prod. Rep. 1992, 243. Rodríguez- Hahn, L.; Esquivel, B.; Cárdenas, J. In Progress in the Chemistry of Organic Natural Products; Herz, W., Kirby, G. W., Moore, R. E., Steglich, W., Tamm, C., Eds.; Springer-Verlag: New York, 1994; Vol. 63, p 107. Piozzi, F. Heterocycles 1994, 37, 603. Piozzi, F.; Bruno, M.; Rosselli, S. Heterocycles 1998, 48, 2185.
4. Merritt, A. T.; Ley, S. V. Nat. Prod. Rep. 1992, 243. Rodríguez- Hahn, L.; Esquivel, B.; Cárdenas, J. In Progress in the Chemistry of Organic Natural Products; Herz, W., Kirby, G. W., Moore, R. E., Steglich, W., Tamm, C., Eds.; Springer-Verlag: New York, 1994; Vol. 63, p 107. Piozzi, F. Heterocycles 1994, 37, 603. Piozzi, F.; Bruno, M.; Rosselli, S. Heterocycles 1998, 48, 2185.
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12. Luteijn, J. M.; de Groot, A. Tetrahedron Lett. 1982, 23, 3421. Jones, P. S.; Ley, S. V.; Simpkins, N. S.; Whittle, A. J. Tetrahedron 1986, 42, 6519. Tokoroyama, T.; Fujimori, K.; Shimizu, T.; Yamagiwa, Y.; Monden, M.; Iio, H. Tetrahedron 1988, 44, 6607. Watanabe, H.; Onoda, T.; Kitahara, T. Tetrahedron Lett. 1999, 40, 2545. Meulemans, T. M.; Stork, G. A.; Macaev, F. Z.; Jansen, B. J. M.; de Groot, A. J. Org. Chem. 1999, 64, 9178.
13. Luteijn, J. M.; de Groot, A. Tetrahedron Lett. 1982, 23, 3421. Jones, P. S.; Ley, S. V.; Simpkins, N. S.; Whittle, A. J. Tetrahedron 1986, 42, 6519. Tokoroyama, T.; Fujimori, K.; Shimizu, T.; Yamagiwa, Y.; Monden, M.; Iio, H. Tetrahedron 1988, 44, 6607. Watanabe, H.; Onoda, T.; Kitahara, T. Tetrahedron Lett. 1999, 40, 2545. Meulemans, T. M.; Stork, G. A.; Macaev, F. Z.; Jansen, B. J. M.; de Groot, A. J. Org. Chem. 1999, 64, 9178.
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16. The term "tethered diacid" refers to compounds such as 4 that consist of two carbon acids connected by a tether.
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18. Grossman, R. B.; Rasne, R. M.; Patrick, B. O. J. Org. Chem. 1999, 64, 7173.
19. 4-Trimethylsilyl-3-butyn-2-one is considerably safer, less expensive, and easier to prepare than 3-butyn-2-one. The double Michael reaction that uses 3-butyn-2-one generated in situ from 4-trimethylsilyl-3-butyn-2-one is therefore much more convenient than the one that uses pure 3-butyn-2-one. Komarov, N. V.; Yarosh, O. G. J. Gen. Chem. USSR (Engl. Transl.) 1967, 37, 247. Walton, D. R. M.; Waugh, F. J. Organomet. Chem. 1972, 37, 45.
20. 4-Trimethylsilyl-3-butyn-2-one is considerably safer, less expensive, and easier to prepare than 3-butyn-2-one. The double Michael reaction that uses 3-butyn-2-one generated in situ from 4-trimethylsilyl-3-butyn-2-one is therefore much more convenient than the one that uses pure 3-butyn-2- one. Komarov, N. V.; Yarosh, O. G. J. Gen. Chem. USSR (Engl. Transl.) 1967, 37, 247. Walton, D. R. M.; Waugh, F. J. Organomet. Chem. 1972, 37, 45.
21. Carroll, F. A. Perspectives on Structure and Mechanism in Organic Chemistry; Brooks/Cole Publishing Co.: Pacific Grove, CA, 1998.
22. Grossman, R. B.; Pendharkar, D. S.; Patrick, B. O. J. Org. Chem. 1999, 64, 7178.
23. 4 is added.
24. van Altena, I. A.; Miller, D. A. Aust. J. Chem. 1989, 42, 2181.
25. New 600 MHz spectra of sacacarin confirm both the reassigned structure and the origin of the misassignment. Maciel, M. A. M. Personal communication.
26. 2 (step 3) and benzene (steps 6 and 10); we have not yet sought alternatives to them at this stage of our research.