New stereospecific synthetic routes to the bicyclo[3.2.1]octane subunit of the kaurenoids and gibberellins

Tetrahedron Letters

Volumn 38, Issue 43, 1997, Pages 7491-7494

  Corey, E J ^a   Liu, Kun ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BICYCLO[3.2.1]OCTANE DERIVATIVE; DITERPENOID;

ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030841351     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01798-X     Document Type: Article

References (18)

1. Goldsmith, D. in The Total Synthesis of Natural Products, ApSimon, J. ed., Wiley-Interscience, New York, Vol VIII, pp 1-243, 1991.
2. Corey, E.J.; Liu, K. J. Am. Chem. Soc. submitted.
3. (a) Corey, E.J.; Danheiser, R.L.; Chandrasekaran, S. J. Org. Chem. 1976, 41, 260.
4. (b) Clark, R.D.; Heathcock, C.H. J. Org. Chem. 1976, 41, 1396.
5. (a) Seyferth, D.; Marmor, R.S.; Hilbert, P.J. J. Org. Chem. 1971, 36, 1379.
6. (b) Gilbert, J.C.; Weeraooriya, U. J. Org. Chem. 1982, 47, 1837.
7. (c) For an improved preparation of this reagent, see: Brown, D.G.; Velthuisen, E.J.; Commerford, J.R.; Brisbois, R.G.; Hoye, T.R. J. Org. Chem. 1996, 61, 2540.
8. (d) For another version of this method, see: Muller, S.; Liepold, B.; Roth, G.J.; Bestmann, H. J. Synlett 1996, 521.
9. For a review see Giese, B.; Angew. Chem. Int. Ed. Engl. 1989, 28, 969.
10. 1,2-Propadienyltriphenylstannane, m.p. 81-82.5 °C, is readily prepared by reaction of propargylmagnesium bromide in ether with triphenylchlorostannane at 23 °C followed by isolation and recrystallization from hexane. See Le Quan, M.; Cadiot, P. Bull. Soc. Chim. Fr. 1965, 45.
11. The propargylation of unhindered, non-β-substituted α,β-enones presents no problems, see (a) Haruta, J.; Nishi, K., Matsuda, S.; Akai, S.; Tamura, Y.; Kita, Y. J. Org. Chem. 1990, 55, 4853.
12. (b) Corey, E.J.; Rücker, C. Tetrahedron Letters 1982, 23, 719.
13. (a) Corey, E.J.; Bass, J.D.; Le Mahieu, R.; Mitra, R.B. J. Am. Chem. Soc. 1964, 86, 5570.
14. (b) Crimmins, M.T.; Reinhold, T.L. Org. React. 1994, 44, 297.
15. 1H NMR data for the epimeric alcohol: C H OH 3.92 δ (ddd, J = 8.0, 6.0, 5.2 Hz, 1 H).
16. 2 2.48 δ (d, J = 12 Hz, 1 H) and 2.18 δ (dt, J = 12.0, 1.9 Hz, 1 H). The H CCl and bridgehead H C dihedral angle for 13 is estimated to be 86°, whereas that for the diastereomeric chloride is expected to be 34° (from measurements with HGS models).
17. 2CC=C at 2.21 δ (d, J = 12.0 Hz, 1 H) and 2.06 δ (d, J = 12.0 Hz, 1 H).
18. This research was supported by grants from the National Institutes of Health and the National Science Foundation.