A novel rearrangement reaction accompanying alkyl metaphosphate extrusion on low-temperature photolysis of 2,3-oxaphosphabicyclo[2.2.2]octene derivatives

Article abstract of DOI:10.1016/0040-4039(92)88077-I

On photolysis in propionitrile or THF solutions at -75°, three phosphonates (1-adamantyl, neopentyl, and ethyl as O-substituents) with the 2,3-oxaphosphabicyclo[2.2.2]octene ring system underwent extensive rearrangement accompanying the usual result at room temperature of metaphosphate extrusion. The rearrangemen product contains a cyclopropane ring, arising from detachment of the bridgehead-bound oxygen followed by attack on the double bond and subsequent ring closure. These rearrangement does not occur with related phosphonamides but has been detected with a phosphine oxide.