J. John, H. Hopf
SHORT COMMUNICATION
Scheme 5. Mechanism for the formation of 3(2H)-furanones.
Conclusions
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In conclusion, we have introduced a new methodology
for the synthesis of substituted 3(2H)-furanones by the re-
action of activated alkenes with 4-chloroacetoacetates un-
der palladium catalysis. The reaction could be tuned to the
formation of either 3(2H)-furanone or diethyl 1,4-dihydrox-
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ycyclohexa-1,4-diene-2,5-dicarboxylate
derivatives
by
changing the temperature. The reaction proceeds through a
catalyzed tandem Michael addition/ring-closing pathway to
afford different 3(2H)-furanones in good to excellent yields.
The products have multiple points of functionalization,
which are currently being studied for different synthetic ma-
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Experimental Section
General Experimental Procedure for the Preparation of Substituted
3(2H)-Furanones: Styrene (1.0 equiv.), Pd(PPh3)4 (5 mol-%), P(o-fu-
ryl)3 (10 mol-%), and K2CO3 (2.0 equiv.) were placed in a Schlenk
tube. The reaction flask was degassed and flushed with argon (3ϫ).
To this mixture, under an atmosphere of argon, was added dioxane
(2 mL) followed by 4-chloroacetoacetate (1.0 equiv.); the mixture
was stirred at 60 °C for 12 h. After completion of the reaction, the
mixture was diluted with dichloromethane (20 mL) and washed
with water (2ϫ20 mL) and saturated brine (20 mL) solution. The
organic layer was then dried with anhydrous magnesium sulfate,
and the solvent was evaporated in vacuo. The residue was chro-
matographed on flash silica gel (ethyl acetate/pentane) to afford the
product in good to excellent yields (see Tables 1 and 2).
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Supporting Information (see footnote on the first page of this arti-
cle): General methods, experimental procedures, and characteriza-
tion data for all new compounds.
Acknowledgments
J. J. thanks the Alexander von Humboldt foundation for a postdoc-
toral fellowship.
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