title: On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
metadata.name: dc.contributor.author
metadata.value: Mereshchenko, Andrey S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Ivanov, Alexey V
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Baranovskii, Viktor I
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Mloston, Grzegorz
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Rodina, Ludmila L
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Nikolaev, Valerij A
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-08T08:42:16Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-08T08:42:16Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015
metadata.lang: -
metadata.name: dc.identifier
metadata.value: 10.3762/bjoc.11.57
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 10.3762/bjoc.11.57
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1977
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: The 1,3-dipolar cycloaddition of acyclic 2-diazo-1,3-dicarbonyl compounds (DDC) and thioketones preferably occurs with Z,E-conformers and leads to the formation of transient thiocarbonyl ylides in two stages. The thermodynamically favorable further transformation of C=S ylides bearing at least one acyl group is identified as the 1,5-electrocyclization into 1,3-oxathioles. However, in the case of diazomalonates, the dominating process is 1,3-cyclization into thiiranes followed by their spontaneous desulfurization yielding the corresponding alkenes. Finally, carbocyclic diazodiketones are much less reactive under similar conditions due to the locked cyclic structure and are unfavorable for the 1,3-dipolar cycloaddition due to the Z,Z-conformation of the diazo molecule. This structure results in high, positive values of the Gibbs free energy change for the first stage of the cycloaddition process.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
metadata.lang: en_GB
resources.filename: Belstein2015_On the strong difference in reactivity of acyclic and cyclic.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/1977/1/Belstein2015_On%20the%20strong%20difference%20in%20reactivity%20of%20acyclic%20and%20cyclic.pdf
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