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Regioselective Palladium-Catalyzed Electrophilic Allylic Substitution in the Presence of Hexamethylditin
journal contribution
posted on 2002-03-27, 00:00 authored by Olov A. Wallner, Kálmán J. SzabóPalladium-catalyzed electrophilic allylic substitution of functionalized allyl chlorides and allyl acetates can be achieved in the presence of
hexamethylditin under mild reaction conditions. The substitution reaction occurs with very high regioselectivity at the branched allylic terminus.
Regioselective tandem bisallylation reaction could be performed by employing benzylidenemalonitrile as substrate. The reaction mechanism
can be explained by involvement of a bisallylpalladium intermediate. A particularly interesting mechanistic feature of this reaction is that
palladium catalyzes up to three different transformations in the same catalytic cycle. DFT calculations indicate that the regioselectivity is
determined by the location of the allylic substituent in the η1-allyl moiety of the reaction intermediate.