A. S.-Y. Lee et al. / Tetrahedron Letters 45 (2004) 1551–1553
1553
recovered when the less reactive indole-3-carboxyalde-
hyde was introduced under the reaction condition
2. Nicolaou, K. C.; Skokotas, G.; Furuya, S.; Suemune, H.;
Nicolaou, D. C. Angew. Chem., Int. Ed. Engl. 1990, 29,
1
064.
(
Table 1, entry 10). Thus, we further investigated that
3
. Fryhle, C. B.; Williard, P. G.; Rybak, C. M. Tetrahedron
Lett. 1992, 33, 2327.
ketone as reacting substrate under this sonochemical
Barbier-type reaction. A series of ketones was investi-
gated under the reaction conditions and the results are
shown in Table 2. Allenyl alcohols were produced as the
minor products in all cases (Table 2). The starting
material was recovered when the less reactive ketone was
reacted under this sonochemical reaction condition.
4. Hirama, M.; Tokuda, M.; Fujiwara, K. Synlett 1991, 651.
5. Chan, T.-H.; Arya, P. Tetrahedron Lett. 1989, 30, 406.
6. Frissen, R. W.; Blouin, M. Tetrahedron Lett. 1997, 38,
4
43.
7. Zhang, L.-J.; Mo, X.-S.; Huang, Y.-Z. J. Organomet.
Chem. 1994, 471, 77.
8
. Araki, S.; Ito, H.; Butsugan, Y. J. Organomet. Chem.
988, 347, 5.
. Brown, H. C.; Khire, U. R.; Narla, G.; Racherla, U. S.
1
In conclusion, this sonochemical Barbier-type reaction
condition provides a simple and facile method for the
synthesis of homopropargyl alcohol with the low con-
tamination of allenyl alcohol. This procedure features
in situ activation of metal to generate propargyl metal,
which reacted with aldehyde or ketone to form homo-
propargyl alcohol after acidic quenching. These results
lead us to apply and expand these homopropargyl alco-
hols to synthesize some biologically active compounds.
9
J. Org. Chem. 1995, 60, 544.
0. Imamoto, T.; Kusumoto, T.; Tawarayama, Y.; Sugiura,
1
1
Y.; Mita, T.; Hatanaka, Y.; Yokoyama, M. J. Org. Chem.
1
984, 49, 3904.
1. Hojo, M.; Sakuragi, R.; Okabe, S.; Hosomi, A. Chem.
Commun. 2001, 357.
12. Han, Y.; Chi, Z.; Huang, Y.-Z. Synth. Commun. 1999, 29,
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1833.
5. Isaac, M. B.; Chan, T.-H. J. Chem. Soc., Chem. Commun.
1
1
1
26
The typical procedure for synthesis of a homoprop-
argyl alcohol is as follows: A reaction mixture of zinc
27
powder (5.0mmol) and 1,2-diiodoethane (1.0mmol),
aldehyde (1.0mmol) and 3-bromo-1-propyne (1.5 mmol)
in anhydrous THF (5.0mL) was sonicated in a com-
1
995, 1003; Tanaka, H.; Hamatani, T.; Yamashita, S.;
Torii, S. Chem. Lett. 1986, 1461.
6. Hojo, M.; Harada, H.; Ito, H.; Hosomi, A. Chem.
Commun. 1997, 2077.
28
mercial ultrasonic cleaning bath
5
(Elma-T490DH,
0kHz) for 2.5 h. After the sonication, an aqueous
1
HCl (2 M, 2 mL/1.0mmol) was added and the filtrate
was extracted with ether (20mL · 3). The combined or-
ganic layer was washed with brine (20mL), dried with
17. Iseki, K.; Kuroki, Y.; Kobayashi, Y. Tetrahedron: Asym-
metry 1998, 9, 2889.
18. Pornet, J. Tetrahedron Lett. 1981, 22, 455.
1
9. Iyoda, M.; Kanao, Y.; Nishizaki, M.; Oda, M. Bull. Chem.
Soc. Jpn. 1989, 62, 3380.
MgSO , filtered and then the organic solvent was re-
4
moved under reduced pressure. Further purification was
achieved on a flash chromatograph with silica gel and
ethyl acetate/hexane as eluant.
2
2
0. Mukaiyama, T.; Harada, T. Chem. Lett. 1981, 621.
1. Nakagawa, T.; Kasatkin, A.; Sato, F. Tetrahedron Lett.
1
995, 36, 3207.
2. Ishiguro, M.; Ikeda, N.; Yamamoto, H. J. Org. Chem.
982, 47, 2225.
3. Lee, A.S.-Y.; Chang, Y.-T.; Wang, S.-H.; Chu, S.-F.
Tetrahedron Lett. 2002, 43, 8489.
2
2
1
Acknowledgements
2
2
4. Lee, A. S.-Y.; Wu, C.-W. Tetrahedron 1999, 55, 12531.
5. Lee, A. S.-Y.; Cheng, R.-Y.; Pan, O.-G. Tetrahedron Lett.
1997, 38, 443.
We thank the National Science Council in Taiwan (NSC
91-2113-M-032-004) and Tamkang University for
financial support.
26. All reagents were purchased from Aldrich and Riedel-
deHaen and all were used directly without further puri-
fication.
2
2
7. The ZnI and ethene were generated from Zn powder and
References and notes
1,2-diiodoethane under sonication.
2
8. The bath should be filled with water containing some 3–
5% detergent. In our laboratory, we used Decon 90, which
permits much more even cavitation in bath water.
1
. Yanagisawa, A.; Habaue, S.; Yamamoto, H. J. Org.
Chem. 1989, 54, 5198.