4
580
M. Mirza-Aghayan et al. / Tetrahedron Letters 44 (2003) 4579–4580
Table 1. Reduction of 1-alkenes using Et SiH/PdCl : 2/0.1
General procedure for reduction of h-olefins
3
2
in ethanol as solvent
To a solution of 1-alkene (0.2 g, 1 equiv.) and triethyl-
silane (2 equiv.) in 10 ml of ethanol was added a
catalytic amount of palladium(II) chloride (10 mol%)
under an argon atmosphere. The resulting mixture was
stirred for 15 h or 1.5 days at room temperature prior
to GC/MS analysis.
Entry
Time (days)
% Yielda
1
1
1
1
1
1
-Octene
-Decene
-Dodecene
-Tetradecene
-Hexadecene
-Octadecene
1
1
1.5
1
1.5
1
100
90
97
73
97
96
a
Determined by GC/MS analysis.
References
1
. (a) Johnstone, R. A. W.; Willby, A. H.; Entwistle, I. D.
Chem. Rev. 1985, 85, 129; (b) Kovacs, J.; Todd, T. D.;
Reibenspies, J. H.; Joo, F.; Darensbourg, D. J.
Organometallics 2000, 19, 3963; (c) Lee, S. H.; Park, Y. J.;
Yoon, C. M. Tetrahedron Lett. 2000, 41, 887.
7
3% (24% isomerized dodecenes were obtained). The
reaction time also has an influence on the product
distribution. The reaction of 1 equiv. of 1-dodecene
with Et SiH/PdCl (2 equiv./10%) for 1.5 days at room
3
2
temperature yielded 97% of n-dodecane. However,
three days were required to obtain a 92% conversion of
2. (a) Chatgilialoglu, C.; Ferreri, C.; Lucarini, M. J. Org.
Chem. 1993, 58, 249; (b) Larson, G. L. In The Chemistry
of Organic Silicon Compounds; Patai, S.; Rappoport, Z.,
Eds.; Wiley: Chichester, UK, 1989; Vol. 1, Chapter 11.
3. (a) Chatgilialoglu, C. Acc. Chem. Res. 1992, 25, 188; (b)
Chatgilialoglu, C. Chem. Rev. 1995, 95, 1229 and refer-
ences cited therein; (c) Keinan, E.; Greenspoon, N. J. Am.
Chem. Soc. 1986, 108, 7314.
1-tetradecene to n-tetradecane.
In summary, this work demonstrates high efficiency for
reduction of alkenes to the corresponding alkanes using
PdCl , triethylsilane and ethanol as solvent, at room
2
temperature. It should be noted that no hydrosilylation
reaction took place during the hydrogenation process
and only the corresponding alkanes were obtained in
high yields.
4. Kursanov, D. N.; Parnes, Z. N.; Bassova, G. I.; Loim, N.
M.; Zdanovich, V. I. Tetrahedron 1967, 23, 2235–2242.
5. Lipowitz, J.; Bowman, S. A. J. Org. Chem. 1973, 38,
162–165.
Experimental
6. Boukherroub, R.; Chatgilialoglu, C.; Manuel, G.
Organometallics 1996, 15, 1508.
All manipulations were carried out under an argon
atmosphere. Ethanol was distilled and stored under
argon. Yields are based on GC/MS analysis using a
FISON GC 8000 series TRIO 1000 gas chromatograph
equipped with a capillary column CP Sil.5 CB, 60
M×0.25 mm Id.
7. Ferreri, C.; Costantino, C.; Chatgilialoglu, C.; Boukher-
roub, R.; Manuel, G. J. Organomet. Chem. 1998, 554,
135–137.
8. Mirza-Aghayan, M.; Boukherroub, R.; Bolourtchian, M.;
Tabar-Hydar K.; Hoseini, M. J. Organomet. Chem.,
accepted for publication.