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.