Chiral tertiary dichloromethylcarbinol derivatives, prepared by stereospecific alpha C-H insertion reaction of dichlorocarbene with protected chiral secondary alcohols, were converted into intermediary alpha-chloroepoxides which gave stereospecifically chiral quaternary carbon compounds, alpha-aminoacids via alpha-azide-aldehydes and alpha-cyanoacetic acids through cyanation, respectively. The fashion generating the quaternary centers from dichloromethylcarbinols via alpha-chloroepoxides was proved to be quite different depending on the substrates: inversion of configuration of non-benzylic substrates and apparent retention with benzylic one.