Enantioselective Synthesis of the Enyne A-Ring Synthon of the 1α-Hydroxy Vitamins D

Journal of Organic Chemistry

Volumn 62, Issue 19, 1997, Pages 6692-6696

  Parker, Kathlyn A ^a   Dermatakis, Apostolos ^a  

^a BROWN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE DERIVATIVE; ALFACALCIDOL; ALKENE DERIVATIVE; ALLYL ALCOHOL; CALCITRIOL; COLECALCIFEROL DERIVATIVE; CYCLOHEXANONE DERIVATIVE; DIMETHYL SULFOXIDE; DOXERCALCIFEROL; KETONE DERIVATIVE; TETRAHYDROFURAN;

ACETYLATION; ARTICLE; CHIRALITY; CIS TRANS ISOMERISM; DISEASE ASSOCIATION; DRUG SYNTHESIS; ENANTIOMER; HYPOCALCEMIA; HYPOPARATHYROIDISM; KIDNEY FAILURE; STEREOCHEMISTRY;

EID: 0030812759     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970957t     Document Type: Article

References (30)

1. Bouillon, R.; Okamura, W.; Norman, A. W. Endocrine Rev. 1995, 16, 200.
2. Zhu, G.-D.; Okamura, W. H. Chem. Rev. 1995, 95, 1877.
3. For more recent contributions, see: (a) Knolker, H.-J.; Ecker, A.; Struwe, P.; Steinmeyer, A.; Muller, G.; Neef, G. Tetrahedron 1997, 53, 91. (b) Yokoyama, H.; Miyamoto, K.; Hirai, Y.; Takahashi, T. Synlett 1997, 187. (c) Posner, G. H.; Dai, H.; Bull, D. S.; Lee, J.-K.; Eydoux, F.; Ishihara, U.; Welsh, W.; Pryor, N.; Petr, S., Jr. J. Org. Chem. 1996, 61, 671. (d) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589.
4. For more recent contributions, see: (a) Knolker, H.-J.; Ecker, A.; Struwe, P.; Steinmeyer, A.; Muller, G.; Neef, G. Tetrahedron 1997, 53, 91. (b) Yokoyama, H.; Miyamoto, K.; Hirai, Y.; Takahashi, T. Synlett 1997, 187. (c) Posner, G. H.; Dai, H.; Bull, D. S.; Lee, J.-K.; Eydoux, F.; Ishihara, U.; Welsh, W.; Pryor, N.; Petr, S., Jr. J. Org. Chem. 1996, 61, 671. (d) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589.
5. For more recent contributions, see: (a) Knolker, H.-J.; Ecker, A.; Struwe, P.; Steinmeyer, A.; Muller, G.; Neef, G. Tetrahedron 1997, 53, 91. (b) Yokoyama, H.; Miyamoto, K.; Hirai, Y.; Takahashi, T. Synlett 1997, 187. (c) Posner, G. H.; Dai, H.; Bull, D. S.; Lee, J.-K.; Eydoux, F.; Ishihara, U.; Welsh, W.; Pryor, N.; Petr, S., Jr. J. Org. Chem. 1996, 61, 671. (d) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589.
6. For more recent contributions, see: (a) Knolker, H.-J.; Ecker, A.; Struwe, P.; Steinmeyer, A.; Muller, G.; Neef, G. Tetrahedron 1997, 53, 91. (b) Yokoyama, H.; Miyamoto, K.; Hirai, Y.; Takahashi, T. Synlett 1997, 187. (c) Posner, G. H.; Dai, H.; Bull, D. S.; Lee, J.-K.; Eydoux, F.; Ishihara, U.; Welsh, W.; Pryor, N.; Petr, S., Jr. J. Org. Chem. 1996, 61, 671. (d) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589.
7. Parker, K. A.; Kim, H.-J. J. Org. Chem. 1992, 57, 752.
8. Alcohol 7 has been isolated from a cis/trans mixture; see Majewski, M; Irvine, N. M.; McKinnon, J. Tetrahedron Asymmetry 1995, 6, 1837.
9. Paulmier, C. Selenium Reagents and Intermediates in Organic Synthesis; Pergamon: New York, 1986; p 132.
10. (a) Sharpless, K. B.; Lauer, R. F. J. Am. Chem. Soc. 1973, 95, 7917.
11. (b) Sharpless, K. B.; Lauer, R. F. J. Am. Chem. Soc. 1972, 94, 7154.
12. (a) Andrews, D. R.; Barton, D. H. R.; Cheng, K. P.; Finet, J.-P.; Hesse, R. H.; Johnson, G.; Pechet, M. M. J. Org. Chem. 1986, 51, 1637.
13. (b) Kiegiel, J.; Wovkulich, P. M.; Uskokovich, M. R. Tetrahedron Lett. 1991, 32, 6057.
14. (a) Ireland, R. E.; Varney, M. D. J. Org. Chem. 1983, 48, 1829.
15. (b) Paquette, L. A.; Maynard, G. D.; J. Am. Chem. Soc. 1992, 114, 5018.
16. (c) Hoffmann, R. W.; Gerlach, R.; Goldmann, S. Tetrahedron Lett. 1978, 29, 2599.
17. (d) Mander, L. N.; Turner, J. V. Aust. J. Chem. 1980, 33, 1559.
18. (e) van Tamelen, E. E.; Taylor, E. G. J. Am. Chem. Soc. 1980, 102, 1202.
19. (f) Mori, K.; Mori, H. Tetrahedron Lett. 1985, 41, 5487.
20. (a) Wadsworth, W. S.; Emmons, W. D. J. Am. Chem. Soc. 1961, 83, 1733.
21. (b) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 8.
22. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P.; Masamune, S.; Roush, W. R.; Sakai, T. Tetrahedron Lett. 1984, 25, 2183.
23. The poor behavior of this substrate in "alkylidenation" had previously been alluded to: see Chen, C.; Crich, D. Tetrahedron 1993, 49, 7943.
24. Crisp, G. T.; Scott, W. J. Synthesis 1985, 335.
25. Logue, M. W.; Teng, K. J. Org. Chem. 1982, 47, 2549.
26. The asymmetrization of ketone 17 was initially attempted by means of Yamamoto's TRIBAL-mediated opening of its (2R,4R)-2,4-pentanediol acetal. The resulting enol ether was converted to α-hydroxy ketone 7 (by way of the bromo ketone trans-5), the Mosher ester of which indicated an optical purity that ranged from 38 to 44% ee. See (a) Yamamoto, H.; Naruse, Y. Tetrahedron Lett. 1986, 27, 1363. (b) Naruse, Y.; Yamamoto, H. Tetrahedron 1988, 44, 6029.
27. The asymmetrization of ketone 17 was initially attempted by means of Yamamoto's TRIBAL-mediated opening of its (2R,4R)-2,4-pentanediol acetal. The resulting enol ether was converted to α-hydroxy ketone 7 (by way of the bromo ketone trans-5), the Mosher ester of which indicated an optical purity that ranged from 38 to 44% ee. See (a) Yamamoto, H.; Naruse, Y. Tetrahedron Lett. 1986, 27, 1363. (b) Naruse, Y.; Yamamoto, H. Tetrahedron 1988, 44, 6029.
28. Subsequent to the completion of our work, Majewski described the enantioselective deprotonation of ketone 17 with a series of chiral bases, obtaining the maximum ee of 90% with the chiral lithium amide 18 and LiCl as an additive; see ref 4 and also Majewski, M.; McKinnon, J. Can. J. Chem. 1994, 72, 1699.
29. Haloketone (-)-5 was converted to the α-hydroxy ketone (-)-7 by the procedure described above. Integration of the NMR spectrum of the Mosher ester of (-)-7 indicated the enantiomeric excess.
30. The allylic alcohol derived from the deacylation of (+)-10 as well as compound (+)-13 were converted to their Mosher esters. Integration of the NMR spectra of these derivatives showed enantiomeric excesses of 82 ± 2%.