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"Three-Component reaction" with aromatic thioketones, phenyl azide, and dimethyl fumarate


Mloston, Grzegorz; Romanski, Jaroslaw; Linden, Anthony; Heimgartner, Heinz (1997). "Three-Component reaction" with aromatic thioketones, phenyl azide, and dimethyl fumarate. Helvetica Chimica Acta, 80:1992-2001.

Abstract

The reaction of thiobenzophenone ( = diphenylmethanethione; 8a) or 9H-fluorene-9-thione (8b) and methyl fumarate (9) in excess PhN3 at 80" yields a mixture of diastereoisomeric thiiranes 10 and 11 (Scheme 1). A mechanism involving the initial formation of 1-phenyl-4,5-dihydro-1H-1,2,3-triazole-4,5-dicarboxylate 12 by 1,3-dipolar cycloaddition of PhN3 and 9 is proposed in Scheme 2.The diazo compound13, which is in equilibrium with 12, undergoes a further 1,3-dipolar cycloaddition with thioketones 8 to give 2,5-dihydro-1,3,4-thiadiazoles 14. Elimination of N2 yields the thiocarbonyl ylide 15 which cyclizes to the corresponding thiirane. Desulfurization of the thiiranes 10 and 11 with hexamethylphosphorous triamide leads to the olefinic compounds 16 (Scheme 3). The crystal structures of 10a, 11a, and 16b were determined.

Abstract

The reaction of thiobenzophenone ( = diphenylmethanethione; 8a) or 9H-fluorene-9-thione (8b) and methyl fumarate (9) in excess PhN3 at 80" yields a mixture of diastereoisomeric thiiranes 10 and 11 (Scheme 1). A mechanism involving the initial formation of 1-phenyl-4,5-dihydro-1H-1,2,3-triazole-4,5-dicarboxylate 12 by 1,3-dipolar cycloaddition of PhN3 and 9 is proposed in Scheme 2.The diazo compound13, which is in equilibrium with 12, undergoes a further 1,3-dipolar cycloaddition with thioketones 8 to give 2,5-dihydro-1,3,4-thiadiazoles 14. Elimination of N2 yields the thiocarbonyl ylide 15 which cyclizes to the corresponding thiirane. Desulfurization of the thiiranes 10 and 11 with hexamethylphosphorous triamide leads to the olefinic compounds 16 (Scheme 3). The crystal structures of 10a, 11a, and 16b were determined.

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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:1997
Deposited On:18 Nov 2013 09:56
Last Modified:05 Apr 2016 17:09
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Polish State Committee for Scientific Research (Grant No. 3 TO9A 15710), Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.19970800617

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