Stereoselective synthesis of the 2,6-disubstituted tetrahydropyran-3-ol of the potent antitumor agent mucocin via an acyl radical cyclization

Tetrahedron Letters

Volumn 38, Issue 30, 1997, Pages 5249-5252

  Evans, P Andrew ^a   Roseman, Jamie D ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTINEOPLASTIC AGENT; RADICAL; TETRAHYDROPYRAN DERIVATIVE;

ARTICLE; CYCLIZATION; DRUG SYNTHESIS; STEREOCHEMISTRY;

EID: 0030857706     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01147-7     Document Type: Article

References (20)

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2. For an alternative approach to the tetrahydropyran ring of mucocin 1, see: Crimmins, M. T.; Rafferty, S. W. Tetrahedron Lett. 1996, 37, 5649.
3. For examples of acyl radicals from acyl selenides, see: (a) Pfenninger, J.; Graf, W. Helv. Chim. Acta 1980, 63, 1562.
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11. 13C-NMR) and analytical (HRMS) data in accord with the assigned structure.
12. 3) for the enantiomer} in 64% overall yield from 10. (equation presented) The sign and magnitude of the rotation was consistent with the Sharpless asymmetric dihydroxylation having given the S,S-enantiomer in ≥90% enantiomeric excess.
13. Maier, M. E.; Reuter, S. Synlett 1995, 1029.
14. Meek, J. S.; Fowler, J. S. J. Org. Chem. 1968, 33, 985.
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16. Batty, D.; Crich, D. Synthesis 1990, 273.
17. Evans, P. A.; Manangan, T. J. Org. Chem. Submitted
18. Curran, D. P.; Porter, N. D.; Giese, B. In Stereochemistry of Radical Reactions: Concepts, Guidelines and Synthetic Applications; VCH Publishers: New York, 1995, pp 77-81.
19. The LUMO of a vinyl sulfone and a vinyl ether are known to have larger coefficients at the β-and α-carbons respectively, thus reinforcing each other in a β-alkoxy vinyl sulfone. See: (a) Sims, J.; Houk, K. N. J. Am. Chem. Soc. 1973, 95, 5798.
20. (b) Fleming, I. Frontier Orbitals and Organic Chemical Reactions, John Wiley and Sons: New York, 1977, p 186.