Selective crystallization of an allylic 7α-bromide: A facile synthesis of (1α,3β)-3-hydroxycholeste-5,7-diene-1,25-diol diacetate

Organic Process Research and Development

Volumn 9, Issue 3, 2005, Pages 306-310

  Van Arnum, Susan D ^a,c   Carpenter, Barry K ^b   Moffet, Harold ^a   Parrish, David R ^a   MacIntrye, Archibald ^a   Cleary, Thomas P ^a   Fritch, Paul ^a  

^a Pharmaceutical Research and Development   (United States)

^b Cornell University ^*  (United States)

^c RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

(1ALPHA,3BETA) 3 HYDROXYCHOLESTE 5,7 DIENE 1,25 DIOL DIACETATE; ACETOACETIC ACID; ACETONITRILE; HYDROCHLORIC ACID; UNCLASSIFIED DRUG;

ARTICLE; CRYSTALLIZATION; DEPROTECTION REACTION; STEREOCHEMISTRY; SYNTHESIS;

EID: 20444466127     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op050009r     Document Type: Article

References (14)

1. Van Arnum, S. D.; Moffet, H.; Carpenter, B. K. Org. Process Res. Dev. 2004, 8, 769-776 and references therein.
2. Daniewski, A. R.; Liu, W.; Okabe, M. Org. Process Res. Dev. 2004, 8, 411-414.
3. Van Arnum, S. D.; Carpenter, B. K.; Parrish, D. R.; MacIntrye, A. J. Org. Chem. 2004, 69, 8529-8532.
4. Uskokovíc, M. R.; Barwid, T. A.; Iacobelli, J. A.; Baggiolini, E. (Hoffmann-La Roche, Inc.). U.S. Patent 3,993,675,1976; Chem. Abstr. 1977, 86, 16846.
5. -1) 3455 (b), 2950 (s), 1740 (s), 1371 (s), 1239 (s).
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7. (b) Takahashi, T.; Nakagawa, N.; Minoshima, T.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1990, 31, 4333-4336.
8. For a review, see: Hirsch, A. L. Vitamin D. In Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; John Wiley & Sons: New York, 1998; Vol. 25, pp 217-256.
9. The following HPLC conditions were used. A Zorbax ODS column with dimensions of 25.0 cm x 4.6 mm was used in conjunction with a mobile phase that consisted of a mixture of 65% acetonitrile and 35% methylene chloride. The flow rate was 0.8 mL/min. A Varex evaporative light-scattering detector (ELSD II) (operating at an exhaust temperature of 40 °C, a heater temperature of 49°C, and a gas flow of 60 mm, 21 psig) was used as a detector. The following retention times were obtained: Ro 21-3245 (2), 3.5 min; Ro 21-5536 (1), 3.8 min, Ro 25-0648 (3) 6.1 min; Ro 25-0650 (6a) 6.6 min; Ro 25-1342 (9) 6.9 min; Ro 24-2495 (4) 7.0 min; Ro 25-0953 (7) 7.4 min; Ro 25-0649 (5) 7.9 min.
10. Kiau, S.; Discordia, R. P.; Madding, G.; Okuniewicz, F. J.; Rosso, V.; Venit, J. J. Org. Chem. 2004, 69, 4256-4261.
11. -1) 2953 (s), 1730 (s), 1237 (s), 1093 (s).
12. -1) 3440 (br), 2943 (s), 1737 (s), 1249 (s).
13. Rappoldt, M. P.; Pauli, L. F.; Hoogendoorn, J. (Duphar International Research B.V.). U.S. Patent 4,464,298, 1984; Chem. Abstr. 1984, 100, 6955.
14. -1) 3481 (b), 2950 (s), 1737 (s), 1245 (s), 611 (w).