446
J.-G. Kim et al.
LETTER
Table 3 One-Pot Synthesis of Conjugated Acetylenic Carboxylatesa (continued)
Br
Ph3P, Br3CCO2Et
THF, reflux
NaNH2, t-BuOK
RCHO
R
CO2Et
CO2Et
r.t., 2 h
R
Entry
14
Aldehyde
Product
Time (h)b
12
Isolated yield (%)
O
57
CO2Et
CO2Et
Me(CH2)6
Me(CH2)6
H
O
H
15
16
12
3
59
O
CO2Et
85
H
a See the typical experimental procedure for the reaction conditions.16
,b
Reaction time for the first step.
c The reaction was carried out with t-BuLi (3.0 equiv).
d The reaction was carried out with t-BuOK (3.0 equiv).
(5) (a) Kobrich, G.; Buck, P. In Chemistry of Acetylenes; Viehe,
H. G., Ed.; Marcel Dekker: New York, 1969, 99.
(b) Schuda, P. F.; Heimann, M. R. J. Org. Chem. 1982, 47,
2484. (c) Kobrich, G. Angew. Chem., Int. Ed. Engl. 1965, 4,
49.
(6) (a) Hendrickson, J. B.; Hussoin, M. S. Synthesis 1989, 217.
(b) Kitazume, T.; Ishikawa, N. Chem. Lett. 1980, 9, 1327.
(7) (a) Barma, D. K.; Kundu, A.; Zhang, H.; Mioskowski, C.;
Falck, J. R. J. Am Chem. Soc. 2003, 125, 3218.
In conclusion, we have established the optimal conditions
for the Wittig reaction for synthesizing a-bromoacrylates,
and developed a simple and efficient one-pot procedure
for preparing conjugated acetylenic carboxylates from al-
dehydes. The availability of a wide variety of aldehydes
may make the present reaction an important tool for pre-
paring the conjugated acetylenic carboxylates.
(b) Ramanarayanan, G. V.; Shukla, V. G.; Akamanchi, K. G.
Synlett 2002, 2059. (c) Forti, L.; Ghelfi, F.; Pagnoni, U. M.
Tetrahedron Lett. 1995, 36, 3023. (d) Kowalski, C. J.;
Weber, A. E.; Fields, K. W. J. Org. Chem. 1982, 47, 5088.
(e) Dunn, G. L.; Dipasquo, V. J.; Hoover, J. R. E. J. Org.
Chem. 1968, 33, 1454. (f) Bordwell, F. G.; Wellman, K. M.
J. Org. Chem. 1963, 28, 2544.
Acknowledgment
This work was supported by the Center for Bioactive Molecular Hy-
brids.
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Synlett 2008, No. 3, 443–447 © Thieme Stuttgart · New York