The first examples of cycloadditions of 2-diazo-1,3-dicarbonyl compounds to aromatic thioketones

(a) [3+2]-Cycloaddition; (b) –N2, [1,5]-electrocyclization; (c) –N2, Wolff rearrangement; [4+2]-cycloaddition. Acyclic 2-diazo-1,3-dicarbonyl compounds react at 20–50°С with aromatic thioketones and through a cascade process, involving the cycloaddition of a diazo group dipole with the CS bond, elim...

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Bibliographic Details
Published in:Tetrahedron letters 2012-06, Vol.53 (24), p.3095-3099
Main Authors: Nikolaev, Valerij A., Ivanov, Alexey V., Shakhmin, Anton A., Sieler, Joachim, Rodina, Ludmila L.
Format: Article
Language:English
Subjects:
1,5-Electrocyclization
2-Diazo-1,3-diazocarbonyl compounds
2-Oxoketenes
Aromatic compounds
Bonding
Cascades
Cycloaddition
Decomposition reactions
Dimers
Dipoles
Oxathioles
Pyrandiones
Tetrahedrons
Thiadiazoline
Thiocarbonyl ylides
Thioketones
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Summary:(a) [3+2]-Cycloaddition; (b) –N2, [1,5]-electrocyclization; (c) –N2, Wolff rearrangement; [4+2]-cycloaddition. Acyclic 2-diazo-1,3-dicarbonyl compounds react at 20–50°С with aromatic thioketones and through a cascade process, involving the cycloaddition of a diazo group dipole with the CS bond, elimination of nitrogen from the arising thiadiazoline, and subsequent [1,5]-electrocyclization of the intermediate СS-ylide, the relevant oxathioles being formed in yields of up to 70%. Carbocyclic 2-diazo-1,3-diketones at room temperature react with thiones much more slowly, but with increasing temperature they partly decompose to produce, via Wolff rearrangement, 2-oxoketenes, which yield [4+2]-cycloaddition products, that is oxathiinones and/or oxoketene dimers.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2012.04.036