Lewis Acid or Alkyl Halide Promoted Rearrangements of Phosphor- and Phosphinimidates to N,N-Disubstituted Phosphor- and Phosphinamidates

Abstract

In this paper, we describe the synthesis of N,N-disubstituted phosphor- and phosphinamidates via alkyl halide or Lewis acid catalyzed rearrangements of phosphor- or phosphinimidates. Furthermore, we introduce a novel one-pot procedure for the synthesis of N,N-disubstituted phosphoramidates which prevents the isolation of potentially explosive alkyl azide derivatives. In this reaction sequence, several alkyl halides are converted in situ into the corresponding azides and reacted with phosphites to generate phosphorimidates. Final addition of a catalytic amount of Lewis acid to the mixture affords the N,N-disubstituted phosphoramidates in good to excellent overall yields.