Breugst, Martin ORCID: 0000-0003-0950-8858, Huisgen, Rolf and Reissig, Hans-Ulrich ORCID: 0000-0002-1912-9635 (2018). Regioselective 1,3-Dipolar Cycloadditions of Diazoalkanes with Heteroatom-Substituted Alkynes: Theory and Experiment. Eur. J. Org. Chem., 2018 (20-21). S. 2477 - 2486. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1099-0690
Full text not available from this repository.Abstract
The 1,3-dipolar cycloadditions of diazomethane and diazoethane with methyl 3-(diethylamino)propiolate were investigated experimentally and computationally by employing density functional theory (DFT). The experiments provided methyl 3-(diethylamino)-pyrazole-4-carboxylates as the only isolated regioisomers. The constitution of these cycloadducts was secured by independent synthesis and decarboxylation to 3-(diethylamino)pyrazoles. The calculations fully support the experimental findings. For the preferred pathway of the diazomethane cycloaddition with the alkyne, a kinetic preference of 9.6 kJmol(-1) was calculated in Et2O solution. The computational analysis was extended to other alkynes, for instance to heteroatom-substituted alkynes such as ethoxyethyne and (ethylthio)ethyne. Again, the calculations nicely explain the switch in regioselectivity of the 1,3-dipolar cycloadditions of diazomethane with these two alkynes, which has been reported earlier by the group of Arens.
Item Type: | Journal Article | ||||||||||||||||
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URN: | urn:nbn:de:hbz:38-182936 | ||||||||||||||||
DOI: | 10.1002/ejoc.201800100 | ||||||||||||||||
Journal or Publication Title: | Eur. J. Org. Chem. | ||||||||||||||||
Volume: | 2018 | ||||||||||||||||
Number: | 20-21 | ||||||||||||||||
Page Range: | S. 2477 - 2486 | ||||||||||||||||
Date: | 2018 | ||||||||||||||||
Publisher: | WILEY-V C H VERLAG GMBH | ||||||||||||||||
Place of Publication: | WEINHEIM | ||||||||||||||||
ISSN: | 1099-0690 | ||||||||||||||||
Language: | English | ||||||||||||||||
Faculty: | Faculty of Mathematics and Natural Sciences | ||||||||||||||||
Divisions: | Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry | ||||||||||||||||
Subjects: | no entry | ||||||||||||||||
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Refereed: | Yes | ||||||||||||||||
URI: | http://kups.ub.uni-koeln.de/id/eprint/18293 |
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