CORDIS provides links to public deliverables and publications of HORIZON projects.
Links to deliverables and publications from FP7 projects, as well as links to some specific result types such as dataset and software, are dynamically retrieved from OpenAIRE .
Exploitable results
For the first time, directed spontaneous resolution of compounds containing asymmetric nitrogen was performed in the way of ahomochiral metal coordinated polymer (complex of 3,3-dimethyldiaziridine withAgNO3) and a H-bonded polymer (l-methoxy-2,2-dicarbamoyl-aziridineand chiral glycoluril with asymmetric C atoms).
The problem of inversion of sterically hindered nitrogen atoms in cyclic hydrazines was developed and solved. For the first time, 1,2-di-sec.-and di-tert.alkyldiaziridines (for 1,2-di-sec.butyldiaziridine ΔGinv= 31 kcal mol-1), 1,3,4-thiadiazolidine and functionally substituted3,4-di-tert.alkyl-1,3,4-oxadiazolidines (ΔGinv = 26 kcal mol-1)were synthesized, the latter were obtained in optically active form.
Stereochemistry of reactions at nitrogen atoms:
Stereodirected N-chlorination of aziridines and bicyclic diaziridines was studied. A new class of organic compounds was obtained: N-fluoroaziridinecarboxylates. New stereoselective method of N-fluorination and nucleophilic substitution at the ester groups were found. A record high barrier of nitrogen inversion (ΔGinv = 35kcal mol-1) was found for methyl-cis-1-fluoroaziridinecarboxylate.Both diastereomerically pure forms of derivatives of1-alkoxyaziridine-2,2-dicarboxylates and1-alkoxy-2,2-bis(trifluoromethyl)aziridines with asymmetric centres at the Natom of the ring and the C atom of the alkoxy substituent were obtained. Basedon X-ray diffraction studies, a correlation of absolute configuration with NMRparameters was found. Chirality transfer from nitrogen to carbon and heteroatoms:
For dimethyl-l-methoxyaziridine-2,2-dicarboxylate the possibility of chirality transfer from N to C atom with the formation of a chiralpolyfunctional synthon was shown.1-Siloxy- and 1-aryloxyaziridine-2,2-dicarboxylates were synthesized for the first time, the latter were obtained in both enantiomeric forms. Novel reactions were discovered: fragmentational heterocyclization of, b-aminoethylaziridine with acetylene dicarboxylates and rearrangement fragmentation of aldoxime to isocyanide. The investigations involved the following spectroscopic methods: dynamic,1H-, 13C-, 15N-, 14N-NMR; PES,IR; UV; MS, ORD, CD. Ab initio and semi-empirical MO calculations were performed.
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