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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Org. Chem. 2007, 72, 14, 5276-5284
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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
https://doi.org/10.1021/jo070685m
Copyright © 2007 American Chemical Society
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Abstract

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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.

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 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 (2a−c, 6a−d, 7−15, and 17−27), and single-crystal X-ray crystallography data. This material is available free of charge via the Internet at http://pubs.acs.org.

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Cited By

This article is cited by 15 publications.

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  2. Przemysław Kalicki, Michał Karchier, Karol Michalak and Jerzy Wicha. Rearrangement of 2,3-Epoxy Alcohol Dimethylthiocarbamate Derivatives. Synthesis of 2,3-Epithio Alcohol Derivatives under Mild Conditions. The Journal of Organic Chemistry 2010, 75 (15) , 5388-5391. https://doi.org/10.1021/jo101000u
  3. Stephen Philip Fearnley and Charnsak Thongsornkleeb. Oxazolone Cycloadducts as Heterocyclic Scaffolds for Alkaloid Construction: Synthesis of (±)-2-epi-Pumiliotoxin C. The Journal of Organic Chemistry 2010, 75 (3) , 933-936. https://doi.org/10.1021/jo902172r
  4. Pawel̷ Chochrek, Jadwiga Frelek, Marcin Kwit and Jerzy Wicha . New Insight into Chiroptical Properties of 1,2-Diols Cyclic Sulfites.. The Journal of Organic Chemistry 2009, 74 (19) , 7300-7308. https://doi.org/10.1021/jo9012964
  5. O. Piva. Five-Membered Rings With Three Oxygen or Sulfur Atoms in 1,2,3-Positions. 2022,,, 120-145. https://doi.org/10.1016/B978-0-12-818655-8.00117-7
  6. Melinda Nonn, Attila Márió Remete, Ferenc Fülöp, Loránd Kiss. Recent advances in the transformations of cycloalkane-fused oxiranes and aziridines. Tetrahedron 2017, 73 (37) , 5461-5483. https://doi.org/10.1016/j.tet.2017.07.062
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  9. Thomas P. Bobinski, Philip L. Fuchs. Citric acid mediated catalytic osmylation/oxidative cleavage of electron deficient olefins: a vinyl sulfone study. Tetrahedron Letters 2015, 56 (28) , 4151-4154. https://doi.org/10.1016/j.tetlet.2015.05.044
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  11. Stuart W. McCombie, William B. Motherwell, Matthew J. Tozer. The Barton-McCombie Reaction. 2012,,, 161-432. https://doi.org/10.1002/0471264180.or077.02
  12. Benedicte Defaut, Thomas B. Parsons, Neil Spencer, Louise Male, Benson M. Kariuki, Richard S. Grainger. Synthesis of the trans-hydrindane core of dictyoxetane. Organic & Biomolecular Chemistry 2012, 10 (25) , 4926. https://doi.org/10.1039/c2ob25384d
  13. Ankita Rai, Atul K. Singh, Pankaj Singh, Lal Dhar S. Yadav. Stereoselective cascade reactions for construction of polyfunctionalised octahydroquinolines via [2C+2C+1C,1N] cyclisation. Tetrahedron Letters 2011, 52 (12) , 1354-1358. https://doi.org/10.1016/j.tetlet.2011.01.079
  14. Li-dong Zhang, Hui-jun Guo, Yang Pan, Fei Qi. Theoretical Study of the AlEt 3 -Promoted Tandem Reductive Rearrangement of Epoxides. Chinese Journal of Chemical Physics 2008, 21 (6) , 547-554. https://doi.org/10.1088/1674-0068/21/06/547-554
  15. Ivan Zlatev, Jean-Jacques Vasseur, François Morvan. Deoxygenation of 5-O-benzoyl-1,2-isopropylidene-3-O-imidazolylthiocarbonyl-α-d-xylofuranose using dimethyl phosphite: an efficient alternate method towards a 3′-deoxynucleoside glycosyl donor. Tetrahedron Letters 2008, 49 (20) , 3288-3290. https://doi.org/10.1016/j.tetlet.2008.03.079

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