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Reaction of 1,2-Di(1-adamantyl)-2-thioxoethanone with Diazomethanes; 1,3- versus 1,5-Dipolar Electrocyclization of a Sterically Crowded Thiocarbonyl S-Methylide


Mloston, G; Urbaniak, K; Nomura, T; Nakayama, J; Heimgartner, H (2009). Reaction of 1,2-Di(1-adamantyl)-2-thioxoethanone with Diazomethanes; 1,3- versus 1,5-Dipolar Electrocyclization of a Sterically Crowded Thiocarbonyl S-Methylide. Polish Journal of Chemistry, 83(11):1945-1951.

Abstract

The reaction of 1,2-di(1-adamantyl)-2-thioxoethanone (4c) with diazomethane and 2-diazopropane yielded 2-acylthiiranes 6a and 6b, respectively, and no 1,3-oxathioles of type 7 were formed. The reaction course is explained via [2+3]-cycloaddition, elimination of N2, and 1,3-dipolar electrocyclization of the intermediate acylsubstituted thiocarbonyl ylides of type 1. The failure of the competitive 1,5-dipolar electrocyclization is a result of the sterically unfavorable conformation of 1a.

The reaction of 1,2-di(1-adamantyl)-2-thioxoethanone (4c) with diazomethane and 2-diazopropane yielded 2-acylthiiranes 6a and 6b, respectively, and no 1,3-oxathioles of type 7 were formed. The reaction course is explained via [2+3]-cycloaddition, elimination of N2, and 1,3-dipolar electrocyclization of the intermediate acylsubstituted thiocarbonyl ylides of type 1. The failure of the competitive 1,5-dipolar electrocyclization is a result of the sterically unfavorable conformation of 1a.

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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:November 2009
Deposited On:25 Nov 2009 15:10
Last Modified:05 Apr 2016 13:33
Publisher:Polskie Towarzystwo Chemiczne
ISSN:0137-5083
Funders:Rector of the University of Lodz, F. Hoffmann-La Roche AG, Basel
Permanent URL: https://doi.org/10.5167/uzh-23969

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