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

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
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Publikationsverlauf

Received: 08. Oktober 2015

Accepted after revision: 04. März 2016

Publikationsdatum:
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.

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