Asymmetrical nonbridgehead nitrogen-XXVI

Alkoxyamines with tertiary N-alkyl substituents were chlorinated to N-chloro-N-alkoxyamines whose reaction with alcohols enabled synthesis of N,N-dialkoxyamines. The DNMR method was used to determine the barriers of inversion of these compounds. Alkaline hydrolysis ( 13 ) followed by subsequent reactions with R -(+)- and S -(−)-α-phenylethylamine yielded diastereomeric salts (+ 29 and − 29 ) whose crystallization and subsequent esterification resulted in optically active acyclic amines (− 13 and + 13 ) with the asymmetric center only at the N atom in the open chain.