Journal of the American Chemical Society
COMMUNICATION
difunctionalization of 1,3-dienes and terminal alkenes. The
conditions are quite simple using reagents that are readily
accessed and are not required in extreme excess. The scope of
this reaction is relatively broad in terms of functional group
compatibility and the products formed would be difficult to
prepare rapidly using current methods. The success of this
reaction class is attributed to the formation of stabilized, cationic
π-allyl-Pd intermediates. In the case of conjugated dienes, the
π-allyl-Pd intermediate is formed initially from Heck insertion of
the alkene, which is faster than Suzuki cross-coupling under the
optimized reaction conditions. In contrast, terminal alkenes
undergo π-allyl-Pd formation by a proposed β-hydride elimina-
tion/Pd-hydride reinsertion rearrangement. The ability to form
sp2ꢀsp3 carbonꢀcarbon bonds on the alkene framework with
different coupling partners holds significant promise for synthetic
endeavors. Future work is focused on probing the synthetic
applications of this reaction class by developing enantioselective
variants, evaluating broad classes of coupling partners, and
understanding the underlying mechanistic features.
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’ ASSOCIATED CONTENT
S
Supporting Information. Experimental procedures and
b
characterization data for new substances. This material is avail-
’ AUTHOR INFORMATION
(10) (a) Jutand, A.; Nꢀegri, S. Organometallics 2003, 22, 4229. (b)
Jutand, A.; Mosleh, A. Organometallics 1995, 14, 1810.
Corresponding Author
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’ ACKNOWLEDGMENT
This work was supported by the National Institutes of Health
(NIGMS RO1 GM3540).
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