Aromatic allylic benzoates are converted to primarily non-conjugated olefinic products when treated with SmI<sub>2</sub>-H<sub>2</sub>O. Selectivities range from 2:1 to 5:1 in favor on the non-conjugated product that we explain with an internal protonation mechanism of an organosamarium intermediate by a coordinated water molecule. Selectivities for the non-conjugated product can be enhanced through the use of methanol as the proton source. Conversely, conjugated products can be selectively formed through the addition of a coordinating amine resulting in an external protonation mechanism.

Ligand- and proton-source effects in samarium(II)-mediated elimination/isomerization reactions of alllylic benzoates

249th National Meeting (2015)

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