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Studies on the reactions of thiocarbonyl s-methanides with hetaryl thioketones


Mloston, Grzegorz; Pipiak, Paulina; Linden, Anthony; Heimgartner, Heinz (2015). Studies on the reactions of thiocarbonyl s-methanides with hetaryl thioketones. Helvetica Chimica Acta, 98(4):462-473.

Abstract

Dihetaryl thioketones react with thiocarbonyl ylides to give 1,3-dithiolanes in high yields. No competitive side reactions of the thiocarbonyl ylides were observed, evidencing the 'superdipolarophilic' character of this less-known group of thioketones. Depending on the type of substituents present in both the thiocarbonyl ylide and the thioketone, formal [3+2] cycloadditions occur with complete regioselectivity or with formation of a mixture of both regioisomers. Regioselective formation of the sterically more crowded 1,3-dithiolanes is explained via a mechanism involving stabilized 1,5-biradicals. In systems with less-efficient radical stabilization, e.g., in the case of adamantanethione S-methanide, substantial violation of the regioselectivity was observed as a result of steric hindrance.

Abstract

Dihetaryl thioketones react with thiocarbonyl ylides to give 1,3-dithiolanes in high yields. No competitive side reactions of the thiocarbonyl ylides were observed, evidencing the 'superdipolarophilic' character of this less-known group of thioketones. Depending on the type of substituents present in both the thiocarbonyl ylide and the thioketone, formal [3+2] cycloadditions occur with complete regioselectivity or with formation of a mixture of both regioisomers. Regioselective formation of the sterically more crowded 1,3-dithiolanes is explained via a mechanism involving stabilized 1,5-biradicals. In systems with less-efficient radical stabilization, e.g., in the case of adamantanethione S-methanide, substantial violation of the regioselectivity was observed as a result of steric hindrance.

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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/ST5/00219
Publisher DOI:https://doi.org/10.1002/hlca.201500057

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