ASYMMETRICAL NONBRIDGEHEAD NITROGEN-XXIV. COMPLETE SEPARATION INTO ANTIPODES AND ABSOLUTE CONFIGURATION OF CHIRALIC N-ALKOXYAZIRIDINES

Article abstract of DOI:10.1016/0040-4020(82)85075-8

Optically active derivates of 1-methoxyaziridine-2,2-dicarboxylic acid have been obtained: the diethyl ester S-(-1a) by kinetic enrichment under the action of 1-ephedrine; the diamides R-(+2d) and S-(-2f) by chrystallisation from methyllactate; the diamide S(-2g) by asymmetric inversion reaction at the N atom while heating in methyllactate.The basic possibility of 1-alkoxyaziridine reactions with retention of optical activity (ammonolysis and reduction with LAH4) has been demonstrated for S-(-1a) and R-(+1). 1-Methoxy-aziridine-2,2-dicarboxylic acid cis-ethyl ester 4 has been completely separated into antipodes 1R,2S-(+4) and 1S,2R-(-4) wich under the effect of diazoethane afford diethyl esters R-(+1) and S-(-1) with optical purity of 96.2 and 93.8percent (determined by PMR using a chiralic shift-reagent).On the basis of X-ray analysis of monoamides of 1-methoxyaziridine-2,2-dicarboxylic acid ethyl ester and of salt +7 the trans-specificity of ammonolysis and hydrolysis of 1 and the absolute configurations of all the optically active derivates obtained were established.