Azabrendanes V. Synthesis and reactions of stereoisomeric exo- and endo-5-aminomethylbicyclo[2.2.1]hept-2-ene-based ureas

• Authors: Lilija Kasyan , Andrey Kasyan , Igor Tarabara , Sergiy Okovytyy , Elena Golodayeva , Andrey Tokar , Yevgeniy Podolyan
• Languages of publication: EN

Abstracts

EN

A number of stereoisomeric ureas (N-[aryl(benzyl, or cycloalkyl)carbamoyl]-exo(endo)-5-aminomethylbicyclo[2.2.1]hept-2-enes) have been synthesized from bicyclo[2.2.1]hept-2-en-exo(endo)-5-carbonitrile by reduction with lithium aluminum hydride and subsequent reaction of the resulting amines with aryl (benzyl, or cycloalkyl) isocyanates. Regioselective alkylation of stereoisomeric ureas has been performed with benzyl chloride under liquid/solid phase-transfer catalysis. The outcome of the reactions of ureas with peroxy acids is dependent upon the orientation of substituents in the bicyclic fragment. Exo-isomeric ureas are transformed into corresponding epoxy-derivatives, while reactions of the endo-isomers are accompanied by intramolecular cyclization, resulting in the formation of azatricyclononane derivatives. Quantum-chemical calculations have established a decisive role for additional hydrogen bonding in the stabilization of transition states in these heterocyclization reactions of ureas. The structures and stereochemical homogeneity of the products have been confirmed by the analysis of 1H and 13C NMR spectra and correlation spectroscopy. The mechanism of the intramolecular heterocyclization reaction of ureas and carboxamide of endo-5-aminomethyl-exo-2,3-epoxybicyclo[2.2.1]heptane series has been studied at the BHandHLYP/6-31G(d) level of theory. [...]

Keywords

EN

Nitrogen-containing heterocycles; Cyclization; Epoxidation; NMR spectroscopy; Density functional theory

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2008
• Volume: 6
• Issue: 2
• Pages: 161-174

Dates

published

1 - 6 - 2008

online

17 - 4 - 2008

Contributors

author

Lilija Kasyan

• Department of Chemistry, Dnepropetrovsk National University, Dnepropetrovsk, 49625, Ukraine

author

Andrey Kasyan

• ProBioGen A.G., D-13086, Berlin, Germany

author

Igor Tarabara

• Department of Chemistry, Dnepropetrovsk National University, Dnepropetrovsk, 49625, Ukraine

author

Sergiy Okovytyy

• Department of Chemistry, Dnepropetrovsk National University, Dnepropetrovsk, 49625, Ukraine

author

Elena Golodayeva

• Department of Chemistry, Dnepropetrovsk National University, Dnepropetrovsk, 49625, Ukraine

author

Andrey Tokar

• Department of Chemistry, Dnepropetrovsk National University, Dnepropetrovsk, 49625, Ukraine

author

Yevgeniy Podolyan

• Department of Chemistry, Jackson State University, Jackson, MS, 39217-0510, USA

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Identifiers

DOI

10.2478/s11532-008-0012-9