A general oxidative cyclization of 1,5-dienes using catalytic osmium tetroxide

Angewandte Chemie - International Edition

Volumn 42, Issue 8, 2003, Pages 948-951

  Donohoe, Timothy J ^a   Butterworth, Sam ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

Cyclization; Heterocycles; Osmium; Oxidation; Synthetic methods

Indexed keywords

CATALYSIS; ISOMERS; OXIDATION; STEREOCHEMISTRY;

OXIDATIVE CYCLIZATION;

ORGANIC COMPOUNDS;

ALKADIENE; OSMIUM TETRAOXIDE; TETRAHYDROFURAN; TRANSITION ELEMENT;

ARTICLE; CATALYST; CHEMICAL INTERACTION; CIS TRANS ISOMERISM; CYCLIZATION; DIHYDROXYLATION; OXIDATION; STEREOCHEMISTRY; STOICHIOMETRY;

EID: 0037463067     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200390253     Document Type: Article

References (23)

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2. E. Klein, W. Rojahn, Tetrahedron 1965, 21, 2353; J. E. Baldwin, M. J. Crossley, E.-M. M. Lehtonen, J. Chem. Soc. Chem. Commun. 1979, 918; D. M. Walba, M. D. Wand, M. C. Wilkes, J. Am. Chem. Soc. 1979, 101, 4396.
3. E. Klein, W. Rojahn, Tetrahedron 1965, 21, 2353; J. E. Baldwin, M. J. Crossley, E.-M. M. Lehtonen, J. Chem. Soc. Chem. Commun. 1979, 918; D. M. Walba, M. D. Wand, M. C. Wilkes, J. Am. Chem. Soc. 1979, 101, 4396.
4. Chromium-promoted cyclization of diols derived from 1,5-diene give the same THF products, see: D. M. Walba, G. S. Stoudt, Tetrahedron Lett. 1982, 23, 727.
5. V. Piccialli, Tetrahedron Lett. 2000, 41, 3731.
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8. T. J. Donohoe, J. J. G. Winter, M. Helliwell, G. Stemp, Tetrahedron Lett. 2001, 42, 971.
9. Compound 5 is known, see: M. E. Jung, I. D. Trifunovich, A. W. Sledeski, Heterocycles 1993, 35, 273. Compound 6 was derivatized to a bis-Moshers ester that was no longer symmetrical; compounds 8, 10, and 11 were characterized by X-ray crystallography. The structure of 7 is assigned by analogy to that of 8, while compound 9 was converted into an authentic sample of 10 by a double Mitsunobu inversion/hydrolysis sequence.
10. Preliminary experiments have shown that both first and second cycle osmium species are capable of undergoing the oxidative cyclization reaction and therefore we find it difficult to discriminate between the two.
11. The pH of these oxidation reactions has been measured at <1; in this range we do not (nor would we expect to) observe asymmetric induction from a chiral cinchona alkaloid ligand. Previous attempts to make the cyclization products enantiopure have used acyl-derived auxiliaries, see: D. M. Walba, C. A. Przybyla, C. B. Walker, Jr., J. Am. Chem. Soc. 1990, 112, 5624; P. J. Kocienski, R. C. D. Brown, A. Pommier, M. Procter, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1998, 9; A. R. L. Cecil, R. C. D. Brown, Org. Lett. 2002, 4, 3715; R. C. D. Brown, C. J. Bataille, R. M. Hughes, A. Kenney, T. J. Luker, J. Org. Chem. 2002, 67, 8079; or chiral phase-transfer catalysis, see: R. C. D. Brown, J. F. Keily, Angew. Chem. 2001, 113, 4628; Angew. Chem. Int. Ed. 2001, 40, 4496.
12. The pH of these oxidation reactions has been measured at <1; in this range we do not (nor would we expect to) observe asymmetric induction from a chiral cinchona alkaloid ligand. Previous attempts to make the cyclization products enantiopure have used acyl-derived auxiliaries, see: D. M. Walba, C. A. Przybyla, C. B. Walker, Jr., J. Am. Chem. Soc. 1990, 112, 5624; P. J. Kocienski, R. C. D. Brown, A. Pommier, M. Procter, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1998, 9; A. R. L. Cecil, R. C. D. Brown, Org. Lett. 2002, 4, 3715; R. C. D. Brown, C. J. Bataille, R. M. Hughes, A. Kenney, T. J. Luker, J. Org. Chem. 2002, 67, 8079; or chiral phase-transfer catalysis, see: R. C. D. Brown, J. F. Keily, Angew. Chem. 2001, 113, 4628; Angew. Chem. Int. Ed. 2001, 40, 4496.
13. The pH of these oxidation reactions has been measured at <1; in this range we do not (nor would we expect to) observe asymmetric induction from a chiral cinchona alkaloid ligand. Previous attempts to make the cyclization products enantiopure have used acyl-derived auxiliaries, see: D. M. Walba, C. A. Przybyla, C. B. Walker, Jr., J. Am. Chem. Soc. 1990, 112, 5624; P. J. Kocienski, R. C. D. Brown, A. Pommier, M. Procter, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1998, 9; A. R. L. Cecil, R. C. D. Brown, Org. Lett. 2002, 4, 3715; R. C. D. Brown, C. J. Bataille, R. M. Hughes, A. Kenney, T. J. Luker, J. Org. Chem. 2002, 67, 8079; or chiral phase-transfer catalysis, see: R. C. D. Brown, J. F. Keily, Angew. Chem. 2001, 113, 4628; Angew. Chem. Int. Ed. 2001, 40, 4496.
14. The pH of these oxidation reactions has been measured at <1; in this range we do not (nor would we expect to) observe asymmetric induction from a chiral cinchona alkaloid ligand. Previous attempts to make the cyclization products enantiopure have used acyl-derived auxiliaries, see: D. M. Walba, C. A. Przybyla, C. B. Walker, Jr., J. Am. Chem. Soc. 1990, 112, 5624; P. J. Kocienski, R. C. D. Brown, A. Pommier, M. Procter, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1998, 9; A. R. L. Cecil, R. C. D. Brown, Org. Lett. 2002, 4, 3715; R. C. D. Brown, C. J. Bataille, R. M. Hughes, A. Kenney, T. J. Luker, J. Org. Chem. 2002, 67, 8079; or chiral phase-transfer catalysis, see: R. C. D. Brown, J. F. Keily, Angew. Chem. 2001, 113, 4628; Angew. Chem. Int. Ed. 2001, 40, 4496.
15. The pH of these oxidation reactions has been measured at <1; in this range we do not (nor would we expect to) observe asymmetric induction from a chiral cinchona alkaloid ligand. Previous attempts to make the cyclization products enantiopure have used acyl-derived auxiliaries, see: D. M. Walba, C. A. Przybyla, C. B. Walker, Jr., J. Am. Chem. Soc. 1990, 112, 5624; P. J. Kocienski, R. C. D. Brown, A. Pommier, M. Procter, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1998, 9; A. R. L. Cecil, R. C. D. Brown, Org. Lett. 2002, 4, 3715; R. C. D. Brown, C. J. Bataille, R. M. Hughes, A. Kenney, T. J. Luker, J. Org. Chem. 2002, 67, 8079; or chiral phase-transfer catalysis, see: R. C. D. Brown, J. F. Keily, Angew. Chem. 2001, 113, 4628; Angew. Chem. Int. Ed. 2001, 40, 4496.
16. The pH of these oxidation reactions has been measured at <1; in this range we do not (nor would we expect to) observe asymmetric induction from a chiral cinchona alkaloid ligand. Previous attempts to make the cyclization products enantiopure have used acyl-derived auxiliaries, see: D. M. Walba, C. A. Przybyla, C. B. Walker, Jr., J. Am. Chem. Soc. 1990, 112, 5624; P. J. Kocienski, R. C. D. Brown, A. Pommier, M. Procter, B. Schmidt, J. Chem. Soc. Perkin Trans. 1 1998, 9; A. R. L. Cecil, R. C. D. Brown, Org. Lett. 2002, 4, 3715; R. C. D. Brown, C. J. Bataille, R. M. Hughes, A. Kenney, T. J. Luker, J. Org. Chem. 2002, 67, 8079; or chiral phase-transfer catalysis, see: R. C. D. Brown, J. F. Keily, Angew. Chem. 2001, 113, 4628; Angew. Chem. Int. Ed. 2001, 40, 4496.
17. 4/TMEDA we have been able to isolate the two (inseparable) osmate ester diastereosiomers shown in Scheme 4 and show that they cyclize to a mixture of 13 and 14.
18. The structures of 13 and 14 were proven by protection of the primary hydroxy groups, desilylation, and oxidation to the C3 ketone. Both 13 and 14 gave the same ketone, which showed reciprocal NOE enhancements between H(C2) and H(C5).
19. S. D. Burke, G. M. Sametz, Org. Lett. 1999, 1, 71.
20. The spectroscopic data from our material matched exactly that in the literature, see: R. Persky, A. Albeck, J. Org. Chem. 2000, 65, 5632.
21. E. Hardegger, F. Lohse, Helv. Chim. Acta 1957, 40, 2383; H. C. Cox, E. Hardegger, F. Kögl, P. Liechti, F. Lohse, C. A. Salemink, Helv. Chim. Acta 1958, 41, 229; E. Hardegger, H. Furter, J. Kiss, Helv. Chim. Acta 1958, 41, 2401.
22. E. Hardegger, F. Lohse, Helv. Chim. Acta 1957, 40, 2383; H. C. Cox, E. Hardegger, F. Kögl, P. Liechti, F. Lohse, C. A. Salemink, Helv. Chim. Acta 1958, 41, 229; E. Hardegger, H. Furter, J. Kiss, Helv. Chim. Acta 1958, 41, 2401.
23. E. Hardegger, F. Lohse, Helv. Chim. Acta 1957, 40, 2383; H. C. Cox, E. Hardegger, F. Kögl, P. Liechti, F. Lohse, C. A. Salemink, Helv. Chim. Acta 1958, 41, 229; E. Hardegger, H. Furter, J. Kiss, Helv. Chim. Acta 1958, 41, 2401.