Various α‐hydrazido phosphonates have been easily prepared on the basis of the nucleophilic addition of diphenyl phosphite to reactive, preformed N‐acylhydrazones and a three‐component (aldehydes, N‐benzoylhydrazide and diphenyl phosphite) coupling reaction through a non‐catalyzed process. An unprecedented and promising enantioselective example of this reaction is also reported.

Uncatalyzed Three-Component Synthesis of α-Hydrazido Phosphonates. -Nucleophilic addition of diphenylphosphite (III) towards preformed (V) or in situ generated N-acylhydrazones proceeds smoothly without the need for catalysts or promoters to give the title hydrazido phosphonates (IV). A first example of an asymmetric version is presented using cinchonidine as catalyst. -(HERRERA*, R. P.; ROCA-LOPEZ, D.; NAVARRO-MOROS, G.; Eur.