A New Reaction Pathway in Organophosphorus Chemistry: Competing SN2 and AE′ Pathways for Nucleophilic Attack at a Phosphorus–Carbon Cage Compound


  • We acknowledge the EPSRC (R.J.K., D.A.P., C.E.W.), the Universities of Bristol (M.G., C.A.R., C.F.) and York (C.E.W., J.M.L.), and The Royal Society (University Research Fellowship for C.A.R.) for financial assistance. We thank Dr. Craig Butts (Bristol) for helpful comments in preparing this manuscript.


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Competition: A combination of 31P NMR spectroscopic and calculational studies have shown that nucleophilic substitution in the phosphorus–carbon cage compound ClP3(CtBu)2 occurs through competing SN2- and AE′-type reaction pathways (see scheme for model compound ClP3(CH)2). The AE′ mechanism results in the formation of a C2v-symmetric intermediate prior to release of the chloride ion.