A. I. Siriwardana et al. / Tetrahedron Letters 44 (2003) 985–987
987
subsequent stereoselective chemical process, while the
transition metal-catalyzed HꢀM addition does not pro-
ceed through intervention of an ionic species but pro-
ceeds via rather neutral organometallic intermediates
which do not possess the biased conformation observed
in the cyclopropylcarbinyl cation, and therefore lead to
diverse regio- and stereoselectivities.
4. (a) Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589; (b)
Carbocyclic Three-Membered Ring Compounds; Houben-
Weyl; de Meijere, A., Ed.; Thieme: Stuttgart, 1996; Vol.
E175.
5. (a) Ko¨ster, R.; Arora, S.; Binger, P. Liebigs Ann. Chem.
1973, 1619; (b) Donskaya, N. A.; Shulishov, E. V.;
Shabarov, Yu. S. J. Org. Chem. USSR 1982, 17, 1874.
6. The reaction was carried out in a well sealed pressure vial.
Therefore, the reaction was conducted at 120°C even using
ether as a solvent.
7. Utimoto, K.; Tamura, M.; Sisido, K. Tetrahedron 1973,
14, 1169.
(3)
8. For a review, (a) Nakamura, I.; Yamamoto. Y. Adv.
Synth. Catal. 2002, 344, 111. For HꢀM addition, (b)
Lautens, M.; Meyer, C.; Lorenz, A. J. Am. Chem. Soc.
1996, 118, 10676; (c) Bessmertnykh, A. G.; Blinov, K. A.;
Grishin, Yu. K.; Donskaya, N. A.; Tveritinova, E. V.;
Yur‘eva, N. M.; Beletskaya, I. P. J. Org. Chem. 1997, 62,
6069; (d) Nishihara, Y.; Itazaki, M.; Osakada, K. Tetra-
hedron Lett. 2002, 43, 2059. For HꢀNu addition, (e)
Tsukada, N.; Shibuya, A.; Nakamura, I.; Yamamoto, Y.
J. Am. Chem. Soc. 1997, 119, 8123; (f) Nakamura, I.;
Itagaki, H.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6458;
(g) Camacho, D. H.; Nakamura, I.; Saito, S.; Yamamoto,
Y. J. Org. Chem. 2001, 66, 270; (h) Nakamura, I.; Saito,
S.; Yamamoto, Y. J. Am. Chem. Soc. 2000, 122, 2661; (i)
Nakamura, I.; Siriwardana, A. I.; Saito, S.; Yamamoto Y.
J. Org. Chem. 2002, 67, 3445; (j) Shi, M.; Xu, B. Org. Lett.
2002, 4, 2145. For MꢀM addition, (k) Ishiyama, T.;
Momota, S.; Miyaura, N. Synlett 1999, 1790; (l) Sugi-
nome, M.; Matsuda, T.; Ito, Y. J. Am. Chem. Soc. 2000,
122, 11015. For RꢀX addition, (m) Fournet, G.; Balme G.;
Gore´, J. Tetrahedron 1988, 44, 5809; (n) Fournet, G.;
Balme, G.; Barieux, J. J.; Gore´, J. Tetrahedron 1988, 44,
5821; (o) Bra¨se, S.; de Meijere, A. Angew. Chem., Int. Ed.
Engl. 1995, 34, 2545; (p) Nu¨ske, H.; Bra¨se, S.;
Kozhushkov, S.; Noltemeyer, M.; Es-Sayed, M.; de Mei-
jere, A. Chem. Eur. J. 2002, 8, 2350. For [3+2] cycloaddi-
tion, (q) Noyori, R.; Odagi, T.; Takaya, H. J. Am. Chem.
Soc. 1970, 92, 5780; (r) Binger, P.; Schuchardt, U. Chem.
Ber. 1981, 114, 3313; (s) Trost, B. M. Angew. Chem. 1986,
98, 1; Angew. Chem., Int. Ed. Engl. 1986, 25, 1; (t) Naka-
mura, I.; Oh, B.-H.; Saito, S.; Yamamoto, Y. Angew.
Chem., Int. Ed. 2001, 40, 1298.
To the best of our knowledge, the present reaction
provides the most general, efficient and direct protocol
for the stereoselective preparation of gem-disubstituted
homoallylic halides; it was rather surprising to us why
such a simple reaction has not been found until now. In
addition to the practical usefulness of the reaction, it is
interesting to compare the mechanisms of the modern
transition metal-catalyzed reactions with a classical
organic reaction.
General experimental procedure of the addition of hydro-
gen chloride to the alkylidenecyclopropane 1b. To the
alkylidenecyclopropane 1b (83.1 mg, 0.5 mmol) was
added 4 M hydrogen chloride in dioxane (0.14 mL, 0.55
mmol) under Ar atmosphere in a pressure vial and the
mixture was stirred at 120°C for 10 min. After comple-
tion of the reaction, which was monitored by GC, the
mixture was filtered through a short silica column with
ethyl acetate as eluent. Purification of the crude
product with silica column chromatography (hexane as
eluent) afforded the homoallylic chloride 2b in 96%
yield.
References
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3. Readily available 5-bromo-2-methyl-2-pentene in Aldrich
and Fluka Companies is very expensive, 11 300 yen/1 g in
Aldrich.
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