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Selenophen-2-yl-substituted thiocarbonyl ylides – at the borderline of dipolar and biradical reactivity


Mloston, Grzegorz; Urbaniak, Katarzyna; Linden, Anthony; Heimgartner, Heinz (2015). Selenophen-2-yl-substituted thiocarbonyl ylides – at the borderline of dipolar and biradical reactivity. Helvetica Chimica Acta, 98(4):453-461.

Abstract

The reactions of aryl (selenophen-2-yl) thioketones with CH2N2 occur with spontaneous elimination of N2, even at low temperature (-65°), to give regioselectively sterically crowded 4,4,5,5-tetrasubstituted 1,3-dithiolanes and/or a novel type of twelve-membered dithia-diselena heterocycles as dimers of the transient thiocarbonyl S-methanides. The ratio of these products depends on the type of substituent located at C(4) of the phenyl ring. Whereas the formation of the 1,3-dithiolanes corresponds to a [3 + 2] cycloaddition of an intermediate thiocarbonyl ylide with the starting thioketone, the twelve-memberd ring has to be formed via dimerization of the 'thiocarbonyl ylide' with an extended biradical structure.

The reactions of aryl (selenophen-2-yl) thioketones with CH2N2 occur with spontaneous elimination of N2, even at low temperature (-65°), to give regioselectively sterically crowded 4,4,5,5-tetrasubstituted 1,3-dithiolanes and/or a novel type of twelve-membered dithia-diselena heterocycles as dimers of the transient thiocarbonyl S-methanides. The ratio of these products depends on the type of substituent located at C(4) of the phenyl ring. Whereas the formation of the 1,3-dithiolanes corresponds to a [3 + 2] cycloaddition of an intermediate thiocarbonyl ylide with the starting thioketone, the twelve-memberd ring has to be formed via dimerization of the 'thiocarbonyl ylide' with an extended biradical structure.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:April 2015
Deposited On:22 Apr 2015 15:12
Last Modified:05 Apr 2016 19:13
Publisher:Wiley-Blackwell Publishing, Inc.
ISSN:0018-019X
Funders:National Science Center (PL-Cracow), Grant Maestro-3, Dec-2012/06/A/ST5/00219
Publisher DOI:https://doi.org/10.1002/hlca.201500050
Permanent URL: https://doi.org/10.5167/uzh-110376

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