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6407
Wovkulich, P. M.; Uskokovic, M. R. Tetrahedron Lett.
1991, 32, 2343; (f) Lautens, M.; Delangho, P. H. M. J.
Org. Chem. 1995, 60, 2474; (g) Charette, A. B.; Beauche-
min, A. J. Organomet. Chem. 2001, 617–618, 702.
6. (a) Concellon, J. M.; Rodriguez-Solla, H.; Gomes, C.
Angew. Chem., Int. Ed. 2002, 41, 1817; (b) Concellon, J.
M.; Rodriguez-Solla, H.; Llanvona, R. J. Org. Chem.
2003, 68, 1132.
7. (a) Lautens, M.; Delanghe, P. H. M. J. Am. Chem. Soc.
1994, 116, 8526; (b) Lautens, M.; Delanghe, P. H. M. J.
Org. Chem. 1993, 58, 5037.
8. (a) Nishino, T.; Watanabe, T.; Okada, M.; Nishiyama, Y.;
Sonoda, N. J. Org. Chem. 2002, 67, 966; (b) Nishino, T.;
Nishiyama, Y.; Sonoda, N. Tetrahedoron Lett. 2002, 43,
3689.
9. Lanthanum powder (278 mg, 2.0 mmol) and iodine
(102 mg, 0.4 mmol) were placed in a two-necked flask.
THF (1 mL), then the alkenes (5.0 mmol) and gem-
dihaloalkanes (1.0 mmol) were added to the flask, and
the mixture was stirred at 67 ꢁC for 5 h under a nitrogen
atmosphere. After the reaction, aq HCl (5%) was added to
the reaction mixture, and the mixture was extracted with
diisopropyl ether (10 mL · 3). The organic layer was
washed with saturated aq sodium thiosulfate
(30 mL · 1), dried over MgSO4 and filtered. The organic
solvent was removed under reduced pressure. Purification
of the residue by HPLC afforded the corresponding
cyclopropanation products. The products were character-
ized by a comparison of their spectra data with those of
authentic samples.
10. In the case of cyclohexene and 2,3-dimethyl-2-butene, the
yields of the cyclopropane derivatives were very low (5%
and 10% yields). It was reported that the relative rate
constants of cyclopropanation of styrene, cyclohexene and
2,3-di methyl-2-butene with CH2BrCl/C4H9Li are 3.7, 1.0
and 0.29. See: (a) Burger, U.; Huisgen, R. Tetrahedron
Lett. 1970, 3049; (b) Huisgen, R.; Burger, U. Tetrahedron
Lett. 1970, 3053; (c) Burger, U.; Huisgen, R. Tetrahedron
Lett. 1970, 3057.
References and notes
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Suckling, C. J. Tetrahedron 1986, 42, 5665; (h) Takeda,
T.; Arai, K.; Shimokawa, H.; Tsubouchi, A. Tetrahedron
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3. For some reviews; see: (a) Preparation of cyclopropyl
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Patai, S., Rappoport, Z., Eds.; Wiley and Sons: New
York, 1987; (b) Salaun, J. Chem. Rev. 1989, 89, 1247.
4. Recently, samarium metal-assisted cyclopropanation of
allylic alcohols,5 a,b-unsaturated amides,6 and a-allenic
alcohols7 with CH2I2 has been reported.
5. (a) Molander, G. A.; Etter, J. B. J. Org. Chem. 1987, 52,
3942; (b) Molander, G. A.; Harring, L. S. J. Org. Chem.
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Kitazume, T. Tetrahedron: Asymmetry 1990, 1, 351; (d)
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