ORGANIC
LETTERS
2011
Vol. 13, No. 9
2402–2405
Ligand-Free Ag(I)-Catalyzed
Carboxylation of Terminal Alkynes
with CO2
Xiao Zhang, Wen-Zhen Zhang,* Xiang Ren, Lin-Lin Zhang, and Xiao-Bing Lu*
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
116012, China
zhangwz@dlut.edu.cn; lxb-1999@163.com
Received March 10, 2011
ABSTRACT
A convenient approach to selectively prepare a wide range of functionalized propiolic acids was developed by AgI-catalyzed carboxylation of
terminal alkynes using carbon dioxide as carboxylative agent under ligand-free conditions.
The development of efficient catalytic processes for CO2
transformation into useful fine chemicals is of great inter-
est and has been a long-standing goal for chemists, since
CO2 is an abundant, inexpensive, and renewable C1
feedstock.1 One of the most promising reactions in this
field is the direct carboxylation of organic compounds with
CO2 to afford carboxylic acids and derivatives. Although
the direct carboxylation of highly reactive organolithium
and Grignard reagents with CO2 can be easily carried out,
it is impossible to synthesize functionalized carboxylic
acids. On the contrary, transition-metal-catalyzed carbox-
ylation of less reactive carbon2ꢀ4 and other nucleophiles5
(5) For examples on transition-metal-catalyzed carboxylation of
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r
10.1021/ol200638z
Published on Web 04/07/2011
2011 American Chemical Society