Abstract
The thermal and photochemical decompositions of three types of optically active alkyl azidoformates (III) were attempted, and it was found in both cases, that optically active 2-oxazolidinones (VI) were obtained with nearly complete retention of configuration. The yield of VI was very low (5%) in the thermal decomposition and moderate (25-30%) in the photochemical one. Considering the relationship between stereospecificity and spin mutiplicity of alkoxycarbonyl nitrene (I), a mechanism was proposed suggesting that the singlet state alkoxycarbonyl nitrene (XXX) generated from III, either by heating or by irradiation, had been inserted into the intramolecular optically active C-H bond through the transition state (XXXII). Moreover, in the course of these studies, the absolute configuration of α-methylphenylglycine (2-amino-2-phenylpropionic acid) was determined using thermal decomposition. Preliminary experiments using racemic compounds were also reported.
