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Three-component reactions with Sterically Crowded 2,2,4,4-Tetramethyl-3-thioxocyclobutanone, Phenyl Azide, and Electron-Deficient C,C-Dipolarophiles


Mloston, Grzegorz; Romanski, Jaroslaw; Linden, Anthony; Heimgartner, Heinz (1996). Three-component reactions with Sterically Crowded 2,2,4,4-Tetramethyl-3-thioxocyclobutanone, Phenyl Azide, and Electron-Deficient C,C-Dipolarophiles. Helvetica Chimica Acta, 79(5):1305-1314.

Abstract

In order to trap ‘thiocarbonyl-aminides’ A, formed as intermediates in the reaction of thiocarbonyl compounds with phenyl azide, a mixture of 2,2,4,4-tetramethyl-3-thioxocyclobutanone ( 1 ) ,phenyl azide, and fumarodinitrile (8) was heated to 80° until evolution of N2 ceased. Two interception products of the ‘thiocarbonyl-aminide’ A (Ar = Ph) were formed: the known 1,4,2-dithiazolidine 3 (cf: Scheme 1 ) and the new 1,2-thiazolidine 12 (Scheme 2). The structure of the latter was established by X-ray crystallography (Fig. 1). The analogous ‘three-component reaction’ with dimethyl fumarate (9) yielded, instead of 8, in addition to the known interception products 3 and 6 (Scheme 1), two unexpected products 15 and 16 (Scheme 3 ), of which the structures were elucidated by X-ray crystallography (Fig. 2). Their formation is rationalized by a primary [2 + 3] cycloaddition of diazo compound 18 with 1 to give 19, followed by a cascade of further reactions (Scheme 4 ) .

Abstract

In order to trap ‘thiocarbonyl-aminides’ A, formed as intermediates in the reaction of thiocarbonyl compounds with phenyl azide, a mixture of 2,2,4,4-tetramethyl-3-thioxocyclobutanone ( 1 ) ,phenyl azide, and fumarodinitrile (8) was heated to 80° until evolution of N2 ceased. Two interception products of the ‘thiocarbonyl-aminide’ A (Ar = Ph) were formed: the known 1,4,2-dithiazolidine 3 (cf: Scheme 1 ) and the new 1,2-thiazolidine 12 (Scheme 2). The structure of the latter was established by X-ray crystallography (Fig. 1). The analogous ‘three-component reaction’ with dimethyl fumarate (9) yielded, instead of 8, in addition to the known interception products 3 and 6 (Scheme 1), two unexpected products 15 and 16 (Scheme 3 ), of which the structures were elucidated by X-ray crystallography (Fig. 2). Their formation is rationalized by a primary [2 + 3] cycloaddition of diazo compound 18 with 1 to give 19, followed by a cascade of further reactions (Scheme 4 ) .

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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:1996
Deposited On:25 Nov 2013 08:18
Last Modified:05 Apr 2016 17:11
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Polish State Committee for Scientific Research (Grant No. 3 TO9A 157 10), Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.19960790507

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