ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
Recently Viewed
You have not visited any articles yet, Please visit some articles to see contents here.
CONTENT TYPES

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

View Author Information
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
Article Views
1625
Altmetric
-
Citations
LEARN ABOUT THESE METRICS
Read OnlinePDF (215 KB)
Supporting Info (3)»

Abstract

Abstract Image

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.

Supporting Information Available

ARTICLE SECTIONS
Jump To

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 http://pubs.acs.org.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By


This article is cited by 15 publications.

  1. Karol Michalak and Jerzy Wicha . Total Synthesis of a CD-Ring: Side-Chain Building Block for Preparing 17-epi-Calcitriol Derivatives from the Hajos–Parrish Dione. The Journal of Organic Chemistry 2011, 76 (16) , 6906-6911. https://doi.org/10.1021/jo201083w
  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
  7. Zhengyuan Xin, Yunlong Lu, Xiaolan Xing, Jingjie Long, Jiabin Li, Xiaowen Xue. Synthesis of (−)-agathic acid and (−)-copalic acid from andrographolide via a regioselective Barton-McCombie reaction. Tetrahedron 2016, 72 (4) , 555-562. https://doi.org/10.1016/j.tet.2015.12.022
  8. Claudio Curti, Nicoletta Brindani, Lucia Battistini, Andrea Sartori, Giorgio Pelosi, Pedro Mena, Furio Brighenti, Franca Zanardi, Daniele Del Rio. Catalytic, Enantioselective Vinylogous Mukaiyama Aldol Reaction of Furan-Based Dienoxy Silanes: A Chemodivergent Approach to γ-Valerolactone Flavan-3-ol Metabolites and δ-Lactone Analogues. Advanced Synthesis & Catalysis 2015, 357 (18) , 4082-4092. https://doi.org/10.1002/adsc.201500705
  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
  10. René Csuk, Anja Barthel-Niesen, Dieter Ströhl, Ralph Kluge, Christoph Wagner, Ahmed Al-Harrasi. Oxidative and reductive transformations of 11-keto-β-boswellic acid. Tetrahedron 2015, 71 (13) , 2025-2034. https://doi.org/10.1016/j.tet.2015.01.062
  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

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE