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

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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
Creators:
CreatorsEmailORCIDORCID Put Code
Breugst, MartinUNSPECIFIEDorcid.org/0000-0003-0950-8858UNSPECIFIED
Huisgen, RolfUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Reissig, Hans-UlrichUNSPECIFIEDorcid.org/0000-0002-1912-9635UNSPECIFIED
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
Uncontrolled Keywords:
KeywordsLanguage
DIAZOCARBONYL COMPOUNDS; MOLECULAR-ENERGIES; REACTIVITY; CHEMISTRY; DIAZOMETHANE; MECHANISM; KINETICS; PROGRAM; AZIDES; ORIGINMultiple languages
Chemistry, OrganicMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/18293

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