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Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

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journal contribution
posted on 14.05.2008, 00:00 by Barry M. Trost, Jia Xie
Inducing absolute stereochemistry in Wagner−Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a π-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C−C bond migration process, our chiral catalysts can control the stereochemistry of both the π-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an α-chiral O-tertiary center which has various synthetic applications.