10.1021/ol0257777.s001 Olov A. Wallner Olov A. Wallner Kálmán J. Szabó Kálmán J. Szabó Regioselective Palladium-Catalyzed Electrophilic Allylic Substitution in the Presence of Hexamethylditin American Chemical Society 2002 allyl moiety reaction conditions functionalized allyl chlorides DFT calculations allyl acetates allylic substituent reaction mechanism η 1 palladium catalyzes substitution reaction Regioselective tandem bisallylation reaction allylic terminus 2002-03-27 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Regioselective_Palladium-Catalyzed_Electrophilic_Allylic_Substitution_in_the_Presence_of_Hexamethylditin/3742548 Palladium-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 η<sup>1</sup>-allyl moiety of the reaction intermediate.