The facile synthetic route to 5- and 6-membered mono and bicyclic 3-cyano-2
-oxo-1,2-thiaphosphacyclanes has been elaborated on the base of intramolecu
lar S-alkylation in a series of mono- and bis-omega -haloalkyl substituted
thiophosphorylacetonitriles. The stereochemistry of the cyclic compounds wa
s determined by NMR as well as X-ray diffraction. The diastereomeric transf
ormations of 3-cyano-2-oxo-1,2-thiaphosphinanes and formation of conglomera
tes in the case of 6-cyano-2-oxa-10-thia-1-phosphabicyclo[4.4.0]decanc-1-ox
ide are discussed.