K. Y. Lee et al. / Tetrahedron Letters 45 (2004) 5043–5046
Table 2. Synthesis of 4-aryl-3-butyne-2-ones 4a–g
5045
Entry
1
Aryl acetylene
Conditions
Products
Yield (%)a
563i;6a
1a
DMA-DMA (2 equiv), DMF, 60–70 °C, 13 h
4a
4b
4cb
COCH3
2
3
1b
1c
DMA-DMA (2 equiv), DMF, 60–70 °C, 12 h
DMA-DMA (2 equiv), DMF, 60–70 °C, 15 h
566c;e
H3C
COCH3
487
H3C(H2C)4
COCH3
4
5
1d
1e
DMA-DMA (2 equiv), DMF, 60–70 °C, 14 h
DMA-DMA (2 equiv), DMF, 80–90 °C, 24 h
4d
5
513i
347
F
COCH3
H3CO
CF3
COOCH3
6
1f
DMA-DMA (2 equiv), DMF, 60–70 °C, 5 h
DMA-DMA (2 equiv), DMF, 40–50 °C, 20h
4f
437
457
COCH3
COCH3
7
1g
4g
N
a References.
b Trace amounts of the corresponding methyl benzoates were contaminated (2–5%).
Org. Lett. 2000, 2, 3849; (f) Tretyakov, E. V.; Tkachev, A.
V.; Rybalova, T. V.; Gatilov, Y. V.; Knight, D. W.;
Vasilevsky, S. F. Tetrahedron 2000, 56, 10075; (g) Serra, S.;
Fuganti, C. Synlett 2002, 1661; (h) Rule, N. G.; Detty, M.
R.; Kaeding, J. E.; Sinicropi, J. A. J. Org. Chem. 1995, 60,
1665; (i) Schubert, T.; Hummel, W.; Kula, M.-R.; Muller,
M. Eur. J. Org. Chem. 2001, 4181; (j) Bouchain, G.; Leit, S.;
Frechette, S.; Khalil, E. A.; Lavoie, R.; Moradei, O.; Woo,
S. H.; Fournel, M.; Yan, Pu T.; Kalita, A.; Trachy-Bourget,
M.-C.; Beaulieu, C.; Li, Z.; Robert, M.-F.; MacLeod, A.
R.; Besterman, J. M.; Delorme, D. J. Med. Chem. 2003, 46,
820; (k) Wadsworth, D. H.; Geer, S. M.; Detty, M. R. J.
Org. Chem. 1987, 52, 3662; (l) Tinnemans, A. H. A.;
Laarhoven, W. H. Tetrahedron 1979, 35, 1537; (m) Howk,
B. W.; Sauer, J. C. J. Am. Chem. Soc. 1958, 80, 4607.
4. For the synthesis of a,b-acetylenic aldehydes, see: (a)
Zanka, A. Org. Proc. Res. Dev. 2000, 4, 46; (b) Comins,
D.; Meyers, A. I. Synthesis 1978, 403; (c) Amaratunga, W.;
Frechet, J. M. J. Tetrahedron Lett. 1983, 24, 1143; (d) Olah,
G. A.; Prakash, G. K. S.; Arvanaghi, M. Synthesis 1984,
228; (e) Olah, G. A.; Arvanaghi, M. Angew. Chem., Int. Ed.
Engl. 1981, 20, 878; (f) Olah, G. A.; Ohannesian, L.;
Arvanaghi, M. J. Org. Chem. 1984, 49, 3856; (g) Gorgues,
A.; Simon, A.; Le Coq, A.; Hercouet, A.; Corre, F.
Tetrahedron 1986, 42, 351; (h) Bobbitt, J. M. J. Org. Chem.
1998, 63, 9367; (i) Cheung, W.-H.; Yu, W.-Y.; Yip, W.-P.;
Zhu, N.-Y.; Che, C.-M. J. Org. Chem. 2002, 67, 7716.
5. For the reverse quenching technique, see: Journet, M.; Cai,
D.; DiMichele, L. M.; Larsen, R. D. Tetrahedron Lett.
1998, 39, 6427.
mechanism for the generation of methyl benzoate
derivatives and the optimized general conditions for the
preparation of the acetylated compounds 4.
In summary, we have developed a convenient synthetic
method for arylpropargyl aldehydes and 4-aryl-3-butyn-
2-ones. Although limited to the arylacetylene derivatives
the method can be used as a good alternative for the
easy access to the arylacetylenic aldehydes and 4-aryl-3-
butyn-2-ones.
Acknowledgements
This study was financially supported by special research
fund of Chonnam National University in 2004.
References and notes
1. Paquette, L. A. In Encyclopedia of Reagents for Organic
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7. Typical procedure for the synthesis of 3a: A mixture of phe-
nylacetylene (1a, 102 mg, 1 mmol) and N,N-dimethylformamide