ORGANIC
LETTERS
2009
Vol. 11, No. 11
2309-2312
Palladium-Catalyzed Decarboxylative
Coupling of Allylic Alkynoates with
Arynes
Shao-Feng Pi, Bo-Xiao Tang, Jin-Heng Li,* Yi-Lin Liu, and Yun Liang*
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research
(Ministry of Education), Hunan Normal UniVersity, Changsha 410081, China
jhli@hunnu.edu.cn; liangyun1972@126.com
Received March 28, 2009
ABSTRACT
A novel and selective protocol for the synthesis of 1-allyl-2-ethynylbenzenes has been developed by palladium-catalyzed decarboxylative
coupling of allylic alkynoates with arynes. This new route allows for both sp-sp2 and sp2-sp3 couplings of allylic alkynoates with arynes in
one pot involving a decarboxylation process.
The transition-metal-catalyzed decarboxylative coupling,
such as the decarboxylative Heck coupling,1 aldol addi-
tions,2 decarboxylative enolate alkylation,3 and decar-
boxylative cross-coupling reactions,4,5 is a useful route for
constructing the carbon-carbon bonds. Among the numerous
transformations, palladium-catalyzed intramolecular decar-
boxylative couplings are particularly interesting because they
often include the challenging sp3 coupling partner via Pd-π-
allyl intermediates.5 Tunge and Rayabarapu, for instance,
have reported a palladium-catalyzed intramolecular decar-
boxylative sp-sp3 coupling of allylic alkynoates to synthesize
1,4-enynes.5a The protocol was conducted via two Pd-π-
allyl intermediates A and B, followed by reductive elimina-
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cross-coupling reactions, see: (a) Gooꢀen, L. J.; Gooꢀen, K.; Rodr´ıguez,
N.; Blanchot, M.; Linder, C.; Zimmermann, B. Pure Appl. Chem. 2008,
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10.1021/ol900643r CCC: $40.75
Published on Web 04/29/2009
2009 American Chemical Society