Efficient, stereoselective synthesis of 24(S),25-epoxycholesterol

Journal of Organic Chemistry

Volumn 63, Issue 26, 1998, Pages 9919-9923

  Tomkinson, Nicholas C O ^a   Willson, Timothy M ^a   Russel, Jonathon S ^b   Spencer, Thomas A ^b  

^a DARTMOUTH COLLEGE   (United States)

^b Dartmouth College ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

24,25 EPOXYCHOLESTEROL; CHOLENIC ACID; CHOLESTEROL DERIVATIVE; DESMOSTEROL ACETATE; STIGMASTEROL; UNCLASSIFIED DRUG;

ARTICLE; CHOLESTEROL SYNTHESIS; DRUG RECEPTOR BINDING; HYDROXYLATION; REGULATORY MECHANISM; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 0032567498     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981753v     Document Type: Article

References (44)

1. Nelson, J. A.; Steckbeck, S. R.; Spencer, T. A. J. Biol. Chem. 1981, 256, 1067-1068.
2. Nelson, J. A.; Steckbeck, S. R.; Spencer, T. A. J. Am. Chem. Soc. 1981, 103, 6974-6975.
3. Spencer, T. A.; Gayen, A. K.; Phirwa, S.; Nelson, J. A.; Taylor, F. R.; Kandutsch, A. A.; Erickson, S. K. J. Biol. Chem. 1985, 260, 13391-13394.
4. Saucier, S. E.; Kandutsch, A. A.; Taylor, F. R.; Spencer, T. A.; Phirwa, S.; Gayen, A. K. J. Biol. Chem. 1985, 260, 14571-14579.
5. Spencer, T. A. Acc. Chem. Res. 1994, 27, 83-90.
6. Sinensky, M.; Logel, J.; Phirwa, S.; Gayen, A. K.; Spencer, T. A. Exp. Cell Res. 1987, 171, 492-497.
7. Janowski, B. A.; Willy, P. J.; Rama Devi, T.; Falck, J. R.; Mangelsdorf, D. A. Nature 1996, 383, 728-731.
8. (a) Lehmann, J. M.; Kliewer, S. A.; Moore, L. B.; Smith-Oliver, T. A.; Oliver, B. B.; Su, J.-L.; Sundseth, S. S.; Winegar, D. A.; Blanchard, D. E.; Spencer, T. A.; Willson, T. M. J. Biol. Chem. 1997, 272, 3137-3140.
9. (b) Peet, D. J.; Turley, S. D.; Ma, W.; Janowski, B. A.; Lobaccaro, J. A.; Hammer, R. E.; Mangelsdorf, D. J. Cell 1998, 93, 693-704.
10. Mark, M.; Müller, P.; Maier, R.; Eisele, B. J. Lipid Res. 1996, 37, 148-158.
11. Morand, O. H.; Aebi, J. D.; Dehmlow, H.; Ji, Y.-H.; Gains, N.; Lengsfeld, H.; Himber, J. J. Lipid Res. 1997, 38, 373-390.
12. Eisele, B.; Budzinski, R.; Müller, P.; Maier, R.; Mark, M. J. Lipid Res. 1997, 38, 564-575.
13. Saucier, S. E.; Kandutsch, A. A.; Gayen, A. K.; Nelson, J. A.; Spencer, T. A. J. Lipid Res. 1990, 31, 2179-2185.
14. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483-2547.
15. Kircher, H. W.; Rosentein, F. U. J. Org. Chem. 1987, 52, 2586-2588. References to other syntheses of desmosterol are provided in this paper.
16. Kris Prasad, V. V.; Ponticorvo, L.; Lieberman, S. J. Steroid Biochem. 1984, 21, 733-736.
17. Okamoto, M.; Tabe, M.; Fujii, T.; Tanaka, T. Tetrahedron: Asymmetry 1995, 6, 767-778.
18. Fagerlund, U. H. M.; Idler, D. R. J. Am. Chem. Soc. 1957, 79, 6473-6475.
19. Shimizu, T.; Osaka, K.; Nakata, T. Tetrahedron Lett. 1997, 38, 2685-2688.
20. Partridge, J. J.; Faber, S.; Uskokovic, M. R. Helv. Chim. Acta 1974, 57, 764-770.
21. Direct conversion of 11 to 13, as reported by Schmittberger and Uguen (Schmittberger, T.; Uguen, D. Tetrahedron Lett. 1996, 37, 29-32) gave poor results in our hands.
22. Dasgupta, S. K.; Crump, D. R.; Gut, M. J. Org. Chem. 1974, 39, 1658-1661.
23. Apfel, M. A. J. Org. Chem. 1978, 43, 2284-2285.
24. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
25. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
26. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
27. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
28. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
29. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
30. Prenyl Grignard reagent (PGR) + 12 or 13: (a) Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444. PGR + 12 + various copper reagents (Cu): (b) Tamura, M.; Kochi, J. Synthesis 1971, 303-305. (c) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 82-83. (d) Schlosser, M. Angew. Chem., Int. Ed. Engl. 1974, 13, 701-706. (e) Reference 25. Prenyllithium (PL): (f) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797-4800. PL + 12 or 13: (g) Reference 22. PL + 12 or 13 + Cu: See ref 23b-d. (h) Lipshutz, B. H.; Elworthy, T. R. J. Org. Chem. 1990, 55, 1695-1696. (i) Lipshutz, B. H.; Ellsworth, E. L.; Dimock, S. H.; Smith, R. A. J. J. Am. Chem. Soc. 1990, 112, 4404-4410.
31. Lithiated 13 + prenyl bromide + Cu: Gorlier, J.-P.; Hamon, L.; Levisalles, J.; Wagnon, J. J. Chem. Soc. Chem. Commun. 1973, 88.
32. Morisaki, M.; Shibata, M.; Duque, C.; Imamura, N.; Ikekawa, N. Chem. Pharm. Bull. 1980, 28, 606-611. This work describes an analogous "backwards" coupling product from the same type of reaction of a C22 tosylate.
33. Dasgupta, S. K.; Gut, M. J. Org. Chem. 1975, 40, 1475-1477. This paper reports that 12 gives only 16 or dimeric product upon reaction with prenyl Grignard reagent. Ikekawa, ref 25, also reports a reduction product analogous to 16.
34. Koch, P.; Nakatani, Y.; Luu, B.; Ourisson, G. Bull. Soc. Chim. Fr. 1983, 189-194.
35. Moriarty, R. M.; Enache, L. A.; Kinney, W. A.; Allen, C. S.; Canary, J. W.; Tuladhar, S. M.; Guo, L. Tetrahedron Lett. 1995, 36, 5139-5142.
36. Atomic coordinates, bond lengths and angles, and thermal parameters for 1 and epi-1 have been deposited at the Cambridge Crystallographic Data Centre, with registration nos. 102766 for 1 and 102765 for epi-1.
37. 3OH at reflux for 24 h, see: Catalan, C. A. N.; Kokke, W. C. M. C.; Duque, C.; Djerassi, C. J. Org. Chem. 1983, 48, 5207-5214.
38. 3OH at reflux for 24 h, see: Catalan, C. A. N.; Kokke, W. C. M. C.; Duque, C.; Djerassi, C. J. Org. Chem. 1983, 48, 5207-5214.
39. Salmond, W. G.; Sobala, M. C. Tetrahedron Lett. 1977, 1695-1698.
40. Boger, D. L.; Coleman, R. S. J. Am. Chem. Soc. 1988, 110, 4796-4807.
41. Gupta, A. S.; Dev, S. J. Chromatogr. 1963, 12, 189-195.
42. Partridge, J. J.; Uskokovic, M. R. U. S. Patent 4,038,272, 1977.
43. Anhydrous 1, mp 160-162°C, has previously been fully characterized: Reference 2. See also: Steckbeck, S. R. PhD Dissertation, Dartmouth College, 1981.
44. Saucier, S. E.; Kandutsch, A. A.; Gayen, A. K.; Swahn, D. K.; Spencer, T. A. J. Biol. Chem. 1989, 264, 6863-6869.