On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation

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 a...

Full description

Bibliographic Details
Main Authors:	Andrey S. Mereshchenko, Alexey V. Ivanov, Viktor I. Baranovskii, Grzegorz Mloston, Ludmila L. Rodina, Valerij A. Nikolaev
Format:	Article
Language:	English
Published:	Beilstein-Institut 2015-04-01
Series:	Beilstein Journal of Organic Chemistry
Subjects:	diazocarbonyl compounds 1,3-dipolar cycloaddition 1,3-oxathioles thiiranes thiocarbonyl ylides thioketones
Online Access:	https://doi.org/10.3762/bjoc.11.57

id	doaj-fbb88b3c0612491c8327977cc4d593f6
record_format	Article
spelling	doaj-fbb88b3c0612491c8327977cc4d593f62021-02-02T04:44:51ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-04-0111150451310.3762/bjoc.11.571860-5397-11-57On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretationAndrey S. Mereshchenko0Alexey V. Ivanov1Viktor I. Baranovskii2Grzegorz Mloston3Ludmila L. Rodina4Valerij A. Nikolaev5Institute of Chemistry, Saint Petersburg State University, University prosp., 26, 198504, Saint Petersburg, RussiaInstitute of Chemistry, Saint Petersburg State University, University prosp., 26, 198504, Saint Petersburg, RussiaInstitute of Chemistry, Saint Petersburg State University, University prosp., 26, 198504, Saint Petersburg, RussiaFaculty of Chemistry, University of Łódź, Tamka 12, 91-403 Łódź, PolandInstitute of Chemistry, Saint Petersburg State University, University prosp., 26, 198504, Saint Petersburg, RussiaInstitute of Chemistry, Saint Petersburg State University, University prosp., 26, 198504, Saint Petersburg, RussiaThe 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.https://doi.org/10.3762/bjoc.11.57diazocarbonyl compounds1,3-dipolar cycloaddition1,3-oxathiolesthiiranesthiocarbonyl ylidesthioketones
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Andrey S. Mereshchenko Alexey V. Ivanov Viktor I. Baranovskii Grzegorz Mloston Ludmila L. Rodina Valerij A. Nikolaev
spellingShingle	Andrey S. Mereshchenko Alexey V. Ivanov Viktor I. Baranovskii Grzegorz Mloston Ludmila L. Rodina Valerij A. Nikolaev On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation Beilstein Journal of Organic Chemistry diazocarbonyl compounds 1,3-dipolar cycloaddition 1,3-oxathioles thiiranes thiocarbonyl ylides thioketones
author_facet	Andrey S. Mereshchenko Alexey V. Ivanov Viktor I. Baranovskii Grzegorz Mloston Ludmila L. Rodina Valerij A. Nikolaev
author_sort	Andrey S. Mereshchenko
title	On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
title_short	On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
title_full	On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
title_fullStr	On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
title_full_unstemmed	On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
title_sort	on the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
publisher	Beilstein-Institut
series	Beilstein Journal of Organic Chemistry
issn	1860-5397
publishDate	2015-04-01
description	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.
topic	diazocarbonyl compounds 1,3-dipolar cycloaddition 1,3-oxathioles thiiranes thiocarbonyl ylides thioketones
url	https://doi.org/10.3762/bjoc.11.57
work_keys_str_mv	AT andreysmereshchenko onthestrongdifferenceinreactivityofacyclicandcyclicdiazodiketoneswiththioketonesexperimentalresultsandquantumchemicalinterpretation AT alexeyvivanov onthestrongdifferenceinreactivityofacyclicandcyclicdiazodiketoneswiththioketonesexperimentalresultsandquantumchemicalinterpretation AT viktoribaranovskii onthestrongdifferenceinreactivityofacyclicandcyclicdiazodiketoneswiththioketonesexperimentalresultsandquantumchemicalinterpretation AT grzegorzmloston onthestrongdifferenceinreactivityofacyclicandcyclicdiazodiketoneswiththioketonesexperimentalresultsandquantumchemicalinterpretation AT ludmilalrodina onthestrongdifferenceinreactivityofacyclicandcyclicdiazodiketoneswiththioketonesexperimentalresultsandquantumchemicalinterpretation AT valerijanikolaev onthestrongdifferenceinreactivityofacyclicandcyclicdiazodiketoneswiththioketonesexperimentalresultsandquantumchemicalinterpretation
_version_	1724305059472211968

On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation

Similar Items