Palladium-catalyzed carbonylation of terminal acetylenes: A new method for synthesis of acetylenecarboxylates

Article abstract of DOI:10.1081/SCC-100000199

Acetylenecarboxylates were easily prepared via palladium bromide-catalyzed carbonylation of terminal acetylenes in fair to good yields.

Full text of DOI:10.1081/SCC-100000199

This article was downloaded by: [Memorial University of Newfoundland]
On: 03 August 2014, At: 15:13
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer
House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
PALLADIUM-CATALYZED CARBONYLATION OF
TERMINAL ACETYLENES: A NEW METHOD FOR
SYNTHESIS OF ACETYLENECARBOXYLATES
Jinheng Li a , Huanfeng Jiang b & Mingcai Chen b
a LCLC, Guangzhou Institute of Chemistry, Chinese Academy of Sciences , P.O. Box 1122,
Guangzhou, 510650, China
b Guangzhou Institute of Chemistry, Chinese Academy of Sciences , LCLC, P.O. Box 1122,
Guangzhou, 510650, China
Published online: 16 Aug 2006.
To cite this article: Jinheng Li , Huanfeng Jiang & Mingcai Chen (2001) PALLADIUM-CATALYZED CARBONYLATION OF
TERMINAL ACETYLENES: A NEW METHOD FOR SYNTHESIS OF ACETYLENECARBOXYLATES, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:2, 199-202, DOI: 10.1081/
SCC-100000199
To link to this article: http://dx.doi.org/10.1081/SCC-100000199
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall
not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other
liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

SYNTHETIC COMMUNICATIONS, 31(2), 199–202 (2001)
PALLADIUM-CATALYZED CARBONYLATION
OF TERMINAL ACETYLENES: A
NEW METHOD FOR SYNTHESIS
OFACETYLENECARBOXYLATES
Jinheng Li, Huanfeng Jiang,∗ and Mingcai Chen
LCLC, Guangzhou Institute of Chemistry, Chinese
Academy of Sciences, P.O. Box 1122,
Guangzhou 510650, China
ABSTRACT
Acetylenecarboxylates were easily prepared via palladium
bromide-catalyzed carbonylation of terminal acetylenes in fair to
good yields.
Palladium-catalyzed carbonylation of alkynes with carbon monoxide has
been known for several years (1–6). Few methods for synthesis of acetylenecar-
boxylates via palladium-catalyzed carbonylation of terminal acetylenes have been
reported (7,8). Generally, acetylenecarboxylates were obtained via the esterifica-
tion of the corresponding acid or alkynes (9–12). Thus, a novel synthesis route to
acetylenecarboxylates is still of considerable interest to synthetic organic chemists.
In this paper, we report a simple and efficient method for synthesis of acetylenecar-
boxylates via palladium bromide-catalyzed carbonylation of terminal acetylenes
(Scheme 1).
∗ To whom correspondence should be addressed.
199
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

200
LI, JIANG, AND CHEN
Scheme 1.
In palladium bromide-catalyzed dicarbonylation of phenylacetylene with
MeOH and CO in MeOH, methyl phenylpropiolate was obtained in fair to good
yield when bases were added. The result encouraged us to use palladium-catalyzed
carbonylation of terminal acetylenes as a general method of acetylenecarboxylate
synthesis. The results of acetylenecarboxylate synthesis using terminal acetylenes,
aliphatic alcohols, and CO in the presence of PdBr2, CuBr2 and bases are summa-
rized in Table 1.
Effects of a series of bases (NaOAc, NaOOCH, Na2CO3, NaHCO3) on
palladium bromide-catalyzed carbonylation of terminal acetylenes were screened
(entries 1–6, Table 1). Addition of NaHCO3 (2 mmol) in the reaction of phenyl-
acetylene with MeOH and CO afforded the highest yields (80%, entry 6). Reac-
tion of 1-heptyne with MeOH and CO also obtained acetylenecarboxylate in a
Table 1. Palladium-Catalyzed Carbonylation of Terminal Acetylenea
Entry
R
Rꢁ
Base
Time (h)
Isolated Yield (%)b
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me
Me
Me
Me
Me
Me
Bu
NaOAc (2 mmol)
NaOAc (3 mmol)
NaOOCH (3 mmol)
Na2CO3 (3 mmol)
NaHCO3 (3 mmol)
NaHCO3 (2 mmol)
NaHCO3 (2 mmol)
NaOAc (3 mmol)
NaOAc (3 mmol)
NaHCO3 (2 mmol)
NaOAc (3 mmol)
NaOAc (3 mmol)
2
2
2
2
2
2
6
6
6
2
6
6
40
65
55
70
75
80
Trace
53
56
83
Bu
Ph
i-Pr
Me
Bu
10
11
12
C5H11
C5H11
C5H11
75
66
i-Pr
aReaction conditions: 1 (1 mmol), 2 (0.6 mL), PdBr2 (0.056 mmol), and CuBr2 (2 mmol)
in alcohol (10 mL) under CO (1 atm) at room temperature.
bIsolated yields.

TERMINAL ACETYLENES
201
good yield (83%, entry 10). However, only traces of acetylenes are converted after
6 h reaction of acetylenes with BuOH or with i-PrOH in the pesence of NaHCO3
(2 mmol) (entry 7). The conversion was complete and the yields were high when
the added base was 3 mmol of NaOAc in stead of NaHCO3 (entry 8, 9, 11, 12).
Reason for the requirement of stronger base in the reaction of acetylenes and BuOH
or i-PrOH is currently under investigation in our laboratory.
In summary, palladium bromide-catalyzed carboalkoxylation of terminal
alkynes reported here offers a simple and efficient method for synthesis of
acetylenecarboxylates.
EXPERIMENTAL
All 1H NMR spectra were recorded at 400 MHz with CDCl3 as a solvent.
TLC was performed using prepared 100–400 mesh silica gel plates (HF254) and
visualization was effected with short wavelength UV light (254 nm). All reagents
were used directly as obtained commercially.
General Procedure for Palladium-Catalyzed
Carboalkoxylation of Terminal Alkynes
To a mixture of PdBr2 (10 mg, 0.056 mmol), CuBr2 (2 mmol), and base in
alcohol (10 mL) were added alkyne 1 (1 mmol) under CO (1 atm). The reaction
mixture was stirred at room temperature for a desired time. After filtration, the
benzene was removed by rotary evaporation to give crude product. Then the
product was purified by preparative TLC on silica gel using light petroleum-ethyl
ether (10:1) as an eluent.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China for finan-
cial support (No. 29772036 and 29872039), and Dr. Fanglu¨ Huang for helpful
discussion.
REFERENCES
1. Larock, R.C. Comprehensive Organic Transformations, VCH Pulishers, Inc.:
New York, 1989; 853.

202
LI, JIANG, AND CHEN
2. Heck, R.F. Palladium Reagents in Organic Syntheses, Academic Press:
London, 1985; 388.
3. Bryndza, H.E.; Tam, W. Chem. Rev. 1988, 88, 1163.
4. Li, J.; Jiang, H. Guangzhou Chemistry (Chinese) 1999, (4), 55.
5. Li, J.; Jiang, H.; Jia, L. Synth. Comm. 1999, 29, 3733.
6. Li, J.; Jiang, H.; Feng, A.; Jia, L. J. Org. Chem. 1999, 64, 5984.
7. Tsuji, J.; Takahashi, M.; Takahashi, T. Tetrahedr. Lett. 1980, 21, 849.
8. Sakurai, Y.; Sakaguchi, S.; Ishii, Y. Tetrahedr. Lett. 1999, 40, 1701.
9. Jung, M.E.; Buszek, K.R. J. Am. Chem. Soc. 1988, 110, 3965.
10. Marshall, J.A.; Andrews, R.C.; Lebioda, L. J. Org. Chem. 1987, 52, 2378.
11. Harris, F.L.; Weiler, L. Tetrahedr. Lett. 1987, 28, 2941.
12. Jung, M.E.; Hagenah, J.A. J. Org. Chem. 1987, 52, 1889.
Accepted April 11, 2000