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Synthesis 2018; 50(13): 2624-2630
DOI: 10.1055/s-0036-1591990
paper
© Georg Thieme Verlag Stuttgart · New York

An Easy Access to Sulfur Derivatives of 6,8-Dioxabicyclo[3.2.1]octanes, Naturally Abundant Scaffolds

Elena Yu. Schmidt
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., 664033 Irkutsk, Russian Federation   Email: boris_trofimov@irioch.irk.ru
,
Ivan A. Bidusenko
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., 664033 Irkutsk, Russian Federation   Email: boris_trofimov@irioch.irk.ru
,
Igor A. Ushakov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., 664033 Irkutsk, Russian Federation   Email: boris_trofimov@irioch.irk.ru
,
Nadezhda I. Protsuk
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., 664033 Irkutsk, Russian Federation   Email: boris_trofimov@irioch.irk.ru
,
Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., 664033 Irkutsk, Russian Federation   Email: boris_trofimov@irioch.irk.ru
› Author AffiliationsThis work was financially supported by a grant from the Russian Scientific Foundation (Project No. 14-13-00588).
Further Information

Publication History

Received: 26 January 2018

Accepted after revision: 21 March 2018

Publication Date:
03 May 2018 (online)

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Abstract

Sulfur derivatives of 6,8-dioxabicyclo[3.2.1]octanes related to a number of natural products have been synthesized by the click hydrothiolation (AIBN or UV irradiation) of 7-methylene-6,8-dioxabicy­clo[3.2.1]octanes, assembled from acetylene and ketones in a one-pot transition-metal-free synthetic operation. An unusual feature of this free-radical reaction is that it is accelerated in the presence of bases due to involvement of the latter in a competition between the thiol addition and proton-catalyzed isomerization of the starting bicyclooctanes.

Key words

6,8-dioxabicyclo[3.2.1]octanes - thiols - vinyl ethers - hydrothiolation

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591990.
  • Supporting Information
 

  • References

    • 1a Kiyota H. Dixon DJ. Luscombe CK. Hettstedt S. Ley SV. Org. Lett. 2002; 4: 3223
      CrossrefPubMed
    • 1b Ren J. Wang J. Tong R. Org. Lett. 2015; 17: 744
      CrossrefPubMed
    • 1c Czubatka-Bienkowska A. Sarnik J. Macieja A. Galita G. Witczak ZJ. Poplawski T. Bioorg. Med. Chem. Lett. 2017; 27: 2713
      CrossrefPubMed
    • 2a Mitchell SS. Rhodes D. Bushman FD. Faulkner DJ. Org. Lett. 2000; 2: 1605
      CrossrefPubMed
    • 2b Marvin CC. Voight EA. Burke SD. Org. Lett. 2007; 9: 5357
      CrossrefPubMed
    • 3a Francke W. Schröder W. Curr. Org. Chem. 1999; 3: 407
    • 3b Yus M. Ramon DJ. Prieto O. Eur. J. Org. Chem. 2003; 2745
  • 4 Vanderwel D. Oehlschlager AC. J. Am. Chem. Soc. 1992; 114: 5081
    Crossref
  • 5 Mori K. Top. Curr. Chem. 2004; 239: 1
    PubMed
  • 6 Gore WE. Pearce GT. Silverstein RM. J. Org. Chem. 1975; 40: 1705
    Crossref
    • 7a Rasmussen LE. L. Greenwood DR. Chem. Senses 2003; 28: 433
      CrossrefPubMed
    • 7b Greenwood DR. Comeskey D. Hunt MB. Rasmussen LE. L. Nature 2005; 438: 1097
      CrossrefPubMed
  • 8 Liu J.-H. Jin Y. Long Y.-Q. Tetrahedron 2010; 66: 1267
    Crossref
  • 9 Zhang W. Tong R. J. Org. Chem. 2016; 81: 2203
    CrossrefPubMed
  • 10 Trofimov BA. Schmidt EYu. Ushakov IA. Mikhaleva AI. Zorina NV. Protsuk NI. Senotrusova EYu. Skital’tseva EV. Kazheva ON. Aleksandrov GG. Dyachenko OA. Eur. J. Org. Chem. 2009; 5142
  • 11 Ananikov VP. Zalesskiy SS. Beletskaya IP. Curr. Org. Synth. 2011; 8: 2
    Crossref
  • 12 Northrop BH. Coffey RN. J. Am. Chem. Soc. 2012; 134: 13804
    CrossrefPubMed
  • 13 Torrents E. Aloy P. Gibert I. Rodriguez-Trelles F. J. Mol. Evol. 2002; 55: 138
    CrossrefPubMed
  • 14 Kolberg M. Strand KR. Graff P. Andersson KK. Biochim. Biophys. Acta 2004; 1699: 1
    CrossrefPubMed
  • 15 Denes F. Pichowicz M. Povie G. Renaud P. Chem. Rev. 2014; 114: 2587
    CrossrefPubMed
  • 16 Nedolya NA. Trofimov BA. Sulfur Rep. 1994; 15: 339
    Crossref
  • 17 Trofimov BA. Schmidt EYu. Bidusenko IA. Cherimichkina NA. Russ. J. Org. Chem. 2016; 52: 1056
    Crossref
  • 18 Schmidt EYu. Trofimov BA. Zorina NV. Mikhaleva AI. Ushakov IA. Skital’tseva EV. Kazheva ON. Alexandrov GG. Dyachenko OA. Eur. J. Org. Chem. 2010; 6727
  • 19 See the Supporting Information for an X-ray structural analysis of major isomer 4b. CCDC 1584866 contains the supplementary crystallographic data for major isomer 4b. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.