The stereochemical lability of P-stereogenic phosphines under conditions of one-electron oxidation is described. Exposure of homochiral P-stereogenic phosphines to catalytic quantities of one-electron acceptors ([NAr3][PF6]) results in complete racemization within minutes at ambient temperature; no loss of stereochemistry is observed in the absence of oxidant under otherwise identical conditions. Mechanistically, the reversible formation of a transient phosphine radical cation, which exhibits a low barrier to pyramidal inversion, is proposed on the basis of electrochemical, kinetic, and computational analysis. The potential synthetic utility of this process will also be described.                                                     

Reactivity of <i>P</i>-stereogenic phosphines in the presence of a one-electron oxidant

244th National Meeting (2012)

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Reactivity of P-stereogenic phosphines in the presence of a one-electron oxidant