38
Virender et al. / Tetrahedron Letters 46 (2005) 37–38
Table 1. Indium-mediated cyclopropanation of olefins with methylene
iodidea
Katsumura, N.; Ito, H.; Butsugan, Y. Tetrahedron Lett.
1989, 30, 1581.
5. (a) Loh, T. P.; Pei, J.; Cao, G. Q. Chem. Commun. 1996,
1819; (b) Kobayashi, S.; Basujima, T.; Nagayama, S.
Tetrahedron Lett. 1998, 39, 1579.
Entry Olefin
Reaction time (h) Yield (%)b
a
b
c
d
e
f
Styrene
5.5
5.0
5.5
4.0
3.75
1.5
1.75
2.5
5.0
8.0
80
85
80
87
85
88
92
90
76
65
50
4-Methylstyrene
3-Methylstyrene
a-Methylstyrene
Methyl methacrylate
Cycloheptene
Cyclohexene
6. (a) Quan, L. G.; Cha, J. K. Chem. Phys. Lipids 2004, 128,
3; (b) Batchelor, R.; Hoberg, J. O. Tetrahedron Lett. 2003,
44, 9043; (c) de Meijere, A. Cyclopropanes: Synthesis,
Houben-Weyl; Thieme: Stuttgart, 1997; (d) Paquette, L. A.
Chem. Rev. 1986, 86, 733; (e) Burgess, K.; Ho, K. K.;
Mye-Sherman, D. Synlett 1994, 575; (f) Falck, J. R.;
Mekonnen, B.; Yu, J.; Lai, J.-Y. J. Am. Chem. Soc. 1996,
118, 6096.
7. (a) Simmons, H. E.; Smith, R. D. J. Am. Chem. Soc. 1958,
80, 5323; (b) Simmons, H. E.; Smith, R. D. J. Am. Chem.
Soc. 1959, 81, 4256; (c) Blanchard, E. P.; Simmons, H. E.
J. Am. Chem. Soc. 1964, 86, 1337; (d) Simmons, H. E.;
Blanchard, E. P.; Smith, R. D. J. Am. Chem. Soc. 1964,
86, 1347; (e) Simmons, H. E.; Cairns, T. L.; Vladuchick, S.
A.; Hoiness, C. M. Org. React. 1973, 20, 1.
g
h
i
Cyclopentene
4-Vinylanisole
4-Chlorostyrene
j
k
trans-Methyl cinnamate 7.5
a Reaction conditions: olefin (1mmol), indium powder (1mmol),
methylene iodide (1.2mmol), acetonitrile (5ml) at room temperature
under a nitrogen atmosphere.
b Isolated yields.
8. (a) Lorenz, J. C.; Long, J.; Yang, Z.; Xue, S.; Xie, Y.;
Shi, Y. J. Org. Chem. 2004, 69, 327; (b) Wittig, G.;
Schwarzenbach, K. Angew. Chem. 1959, 71, 652; (c)
Wittig, G.; Wingler, F. Liebigs Ann. Chem. 1962, 656, 18;
(d) Wittig, G.; Jautelant, M. Liebigs Ann. Chem. 1967,
702, 24.
9. (a) Molander, G. A.; Etter, J. B. J. Org. Chem. 1987, 52,
3942; (b) Molander, G. A.; Harring, L. S. J. Org. Chem.
1989, 54, 3525.
for this reaction from the point of view of yields. The
mechanism of the reaction is not clear at this stage;
the reaction probably involves the formation of
an organoindium-halide species by the reaction of
methylene iodide and metallic indium13 followed by its
reaction with the olefin to yield the cyclopropane.
In conclusion, we have described a new and highly effi-
cient indium-mediated cyclopropanation of olefins in
very good yields under mild conditions.
10. Maruoka, K.; Fukutani, Y.; Yamamoto, H. J. Org. Chem.
1985, 50, 4412.
11. (a) Jain, S. L.; Sain, B. Angew. Chem., Int. Ed. 2003, 42,
1265; (b) Jain, S. L.; Sain, B. Chem. Commun. 2002, 1040;
(c) Sharma, V. B.; Jain, S. L.; Sain, B. Tetrahedron Lett.
2003, 44, 383; (d) Jain, S. L.; Sain, B. J. Mol. Catal. 2001,
176, 101; (e) Sharma, V. B.; Jain, S. L.; Sain, B.
Tetrahedron Lett. 2003, 44, 3235; (f) Jain, S. L.; Sharma,
V. B.; Sain, B. Tetrahedron Lett. 2003, 44, 4385; (g) Jain,
S. L.; Sharma, V. B.; Sain, B. Tetrahedron Lett. 2004, 45,
1233.
Acknowledgements
We thank the Director, IIP for his kind permission to
publish these results. Virender and S.L.J. thank CSIR,
New Delhi for the award of Research Fellowships.
12. Typical experimental procedure: To a stirred mixture of
cyclohexene (82mg, 1mmol) and indium metal (114mg,
1mmol) in acetonitrile (5ml) was added methylene iodide
(320mg, 1.2mmol) drop by drop under a nitrogen
atmosphere at 25°C. Stirring was continued until the
reaction mixture appeared turbid. After completion, the
reaction mixture was filtered followed by evaporation of
the solvent. The residue obtained was purified by passing
through a short silica gel column using hexane/ethyl
acetate (4:1) as eluent. Evaporation of the solvent yielded
bicyclo[4.1.0]heptane (86mg, 92%). Other cyclopropanes
were prepared similarly, their reaction times and yields are
presented in the Table 1.
References and notes
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Boca Raton FL, 1993.
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J. Organomet. Chem. 1989, 369, 291; (b) Araki, S.;
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Organomet. Chem. 1972, 40, C9.