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Synthesis of New 18-Substituted Analogues of Calcitriol Using a Photochemical Remote Functionalization

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Departamento de Química Fundamental, Universidade da Coruña, E-15071 A Coruña, Spain, and Departamento de Química Orgánica y Unidad Asociada al CSIC, Universidade de Santiago de Compostela, E-15706 Santiago de Compostela, Spain
Cite this: J. Org. Chem. 2002, 67, 14, 4707–4714
Publication Date (Web):May 23, 2002
https://doi.org/10.1021/jo020022z
Copyright © 2002 American Chemical Society
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Abstract

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A novel convergent synthetic approach to new analogues of calcitriol modified at the C-18 position is reported. The key step in the synthesis is the 20-hydroxyl-directed photochemical iodination of the 18-methyl group in the presence of (diacetoxyiodo)benzene. Using this methodology, two new analogues of calcitriol were prepared:  the first contains a hydroxylated alkyl side chain attached at C-18 with the natural side chain replaced by an isopropylidene group; the second is a conformationally locked analogue due to an extra oxacycle between the C-18 and C-20 positions.

 Universidade da Coruña.

 Universidade de Santiago de Compostela.

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1H and 13C NMR spectra for all new compounds. Experimental procedure for the preparation of 30 and X-ray data. This material is available free of charge via the Internet at http://pubs.acs.org.

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  11. 重阳 刘. Advances on Synthesis of 1α,25-Dihydroxyvitamin D3 and Related Analogues. Journal of Organic Chemistry Research 2014, 02 (01) , 1-12. https://doi.org/10.12677/JOCR.2014.21001
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  14. Frederik De Buysser, Lieve Verlinden, Annemieke Verstuyf, Pierre J. De Clercq. Synthesis of 22-oxaspiro[4.5]decane CD-ring modified analogs of 1α,25-dihydroxyvitamin D3. Tetrahedron Letters 2009, 50 (28) , 4174-4177. https://doi.org/10.1016/j.tetlet.2009.05.005
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  20. Xue-Long Hou, Zhen Yang, Henry N.C. Wong. Chapter 5.3 Five-membered ring systems: Furans and benzofurans. 2003,,, 167-205. https://doi.org/10.1016/S0959-6380(03)80010-7
  21. Mary K. Boyd, Garrett M. Zopp. 11  Organic photochemistry. Annual Reports Section "B" (Organic Chemistry) 2003, 99 , 396. https://doi.org/10.1039/b212013p

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