Synlett 2016; 27(11): 1653-1658
DOI: 10.1055/s-0035-1561594
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© Georg Thieme Verlag Stuttgart · New York

Unexpected Regioselective Reactions of 2-Bromomethyl-1,3-thiaselenole with Dithiocarbamates: The First Example of Nucleophilic Attack at Selenium Atom of Seleniranium Intermediate

Authors

  • Svetlana V. Amosova*

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Maxim V. Penzik

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Vladimir A. Potapov

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Andrey S. Filippov

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Vladimir A. Shagun

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Aleksander I. Albanov

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Tatyana N. Borodina

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
  • Vladimir I. Smirnov

    A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Science, 1 Favorsky Str., Irkutsk 664033, Russian Federation   Email: amosova@irioch.irk.ru
Further Information

Publication History

Received: 08 October 2015

Accepted after revision: 04 March 2016

Publication Date:
12 April 2016 (online)


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Abstract

The regio- and stereoselective reaction of 2-bromomethyl-1,3-thiaselenole with sodium N,N-dialkyl dithiocarbamates is accomplished at room temperature for two minutes in MeCN to afford (Z)-2-{[(dialkylamino)carbothioyl]sulfanylselanyl}ethenyl vinyl sulfides in up to 98% yield. At a longer time (8 h), the reaction regioselectively gives 2,3-dihydro-1,4-thiaselenin-2-yl N,N-dialkylcarbamodithioates in high yields. The latter are formed by rearrangement of the former compounds. DFT calculations show that the reactions proceed via a seleniranium intermediate. The formation of the products is the result of nucleophilic attacks of dithiocarbamate anion either at the selenium atom or at the carbon-2 atom of the seleniranium cation. The reaction leading to sulfanylselanylethenyl vinyl sulfides represents the first example of nucleophilic attack at the selenium atom of seleniranium intermediate.

Supporting Information