American Chemical Society
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Unexpected Benzylic Carbon−Carbon Bond Cleavage by Transfer Epizirconation:  Indications of an SET Pathway and Implications for Alkane Metathesis1

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journal contribution
posted on 2005-12-19, 00:00 authored by John J. Eisch, Somnath Dutta, John N. Gitua
In addition to the zirconation of benzylic hydrocarbons, Ar−CH3, by di-n-butylzirconium diethoxide and the ensuing C−C bond formation from (Ar−CH2)2Zr(OEt)2 to yield Ar−CH2−CH(ZrH(OEt)2)−Ar, it has now been found that Bu2Zr(OEt)2 in ethers can also cleave the C−C bond in bibenzylic hydrocarbons, Ar−CH2−CH2−Ar‘, into benzylic zirconium fragments, (Ar−CH2)(Ar‘−CH2)Zr(OEt)2, as fostered by LiOEt and donor solvents. The role of SET processes in such C−C bond cleavages and the potential relevance to practical alkane metathesis are considered.