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 Affiliations
This 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)


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.

Supporting Information