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Résultats exploitables
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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