Пожалуйста, используйте этот идентификатор, чтобы цитировать или ссылаться на этот ресурс:
http://hdl.handle.net/11701/1977
Полная запись метаданных
Поле DC | Значение | Язык |
---|---|---|
dc.contributor.author | Mereshchenko, Andrey S | - |
dc.contributor.author | Ivanov, Alexey V | - |
dc.contributor.author | Baranovskii, Viktor I | - |
dc.contributor.author | Mloston, Grzegorz | - |
dc.contributor.author | Rodina, Ludmila L | - |
dc.contributor.author | Nikolaev, Valerij A | - |
dc.date.accessioned | 2016-04-08T08:42:16Z | - |
dc.date.available | 2016-04-08T08:42:16Z | - |
dc.date.issued | 2015 | - |
dc.identifier | 10.3762/bjoc.11.57 | - |
dc.identifier.issn | 10.3762/bjoc.11.57 | - |
dc.identifier.uri | http://hdl.handle.net/11701/1977 | - |
dc.description.abstract | 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. | en_GB |
dc.language.iso | en | en_GB |
dc.title | On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation | en_GB |
Располагается в коллекциях: | Articles |
Файлы этого ресурса:
Файл | Описание | Размер | Формат | |
---|---|---|---|---|
Belstein2015_On the strong difference in reactivity of acyclic and cyclic.pdf | 969,96 kB | Adobe PDF | Просмотреть/Открыть |
Все ресурсы в архиве электронных ресурсов защищены авторским правом, все права сохранены.