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Expedited Approach to the Vitamin D trans-Hydrindane Building Block from the Hajos Dione. Comparative Study on Various Methods for the Selective Deoxygenation of One of the Hydroxy Groups in a Diol

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Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw 48, Poland
Cite this: J. Org. Chem. 2007, 72, 14, 5276–5284
Publication Date (Web):June 19, 2007
Copyright © 2007 American Chemical Society
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1α,25-Dihydroxyvitamin D3 (calcitriol, 1) is a bioregulator important for the treatment of various human metabolic diseases and biomedical research. Herein, we report an efficient diastereoselective approach to the key trans-hydrindane building block for calcitriol synthesis (2a) starting from the readily accessible optically active tetrahydroindenedione derivative (Hajos dione, 3). It was found that epoxide ring opening in a related hydroxy epoxide (7) with sodium cyanoborohydride−BF3 × Et2O occurs by hydride anion addition at the ring juncture position to produce a vicinal diol with the trans-hydrindane ring system (6a). Four methods for selective deoxygenation of the sterically less shielded hydroxy group in diol 6a were examined with an approach based on a cyclic sulfate of the diol as the most efficient and operationally convenient method.


 Corresponding author. Tel.:  48-22-632-8117; fax:  48-22-632-6681.

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Description of general experimental methods, 1H and 13C NMR spectra of all new compounds (2ac, 6ad, 715, and 1727), and single-crystal X-ray crystallography data. This material is available free of charge via the Internet at

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This article is cited by 15 publications.

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