The selectivity of the substitution reaction of phosphoryl chloride with organometallic
reagents was investigated using NMR spectroscopy. This led to the discovery that the
selectivity of the substitution reaction can be tuned by choosing a proper organometallic
reagent. A phosphinate could be obtained by using a Grignard reagent whereas an organozinc
reagent provided a phosphonate. Based on these results, one-pot synthetic methods
for the preparation of phosphinates and phosphonates using commercially available
starting materials were developed. Both methods allow the synthesis of a broad range
of either phosphinate or phosphonate derivatives in a straightforward and general
procedure. Moreover, using these one-pot procedures, mixed systems substituted with
different alkyl/aryl groups can be prepared.
Key words
selectivity - substitution - phosphoryl chloride - phosphinate - phosphonate - Grignard
reagent - organozinc reagent
