Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P ⋅ BPh ] (Mes*=2,4,6-tBu C H ) are reported. The reactions proceed by extrusion of a P fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P , which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels-Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P - and P -containing organophosphorus compounds in two simple steps from white phosphorus.
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