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  • Title: Palladium-catalyzed electrophilic substitution of allyl chlorides and acetates via bis-allylpalladium intermediates.
    Author: Wallner OA, Szabó KJ.
    Journal: J Org Chem; 2003 Apr 04; 68(7):2934-43. PubMed ID: 12662072.
    Abstract:
    Palladium-catalyzed electrophilic allylic substitution of functionalized allyl chlorides and allyl acetates can be achieved in the presence of hexamethylditin under mild and neutral reaction conditions. This efficient one-pot procedure involves palladium-catalyzed formation of transient allylstannanes followed by generation of a bis-allylpalladium intermediate, which subsequently reacts with electrophiles. Using this catalytic transformation, various aldehydes and imines can be allylated providing highly functionalized homoallyl alcohols and amines. Furthermore, tandem bis-allylation reactions could be performed by employing tosyl isocyanate and benzylidenemalonitrile as substrates. A particularly interesting mechanistic feature of this reaction is that palladium catalyzes up to three different transformations in each catalytic cycle. Various allylic functionalities, including COOEt, CONH(2), COCH(3), CN, Ph, and CH(3), are tolerated in the catalytic reactions due to the application of neutral and mild reaction conditions. The substitution reaction occurs with very high regioselectivity at the branched allylic terminus. Moreover, in several reactions, a high stereoselectivity was observed indicating that this new catalytic process has a high potential for stereoselective synthesis. The regioselectivity of the reaction can be explained on the basis of DFT calculations. These studies indicate that the allylic substituent prefers the gamma-position of the eta(1)-allyl moiety of the reaction intermediate.
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