1074
LETTERS
SYNLETT
To know the reactivity of aryl substituted epoxides, styrene oxide was
Ishiyama, K.; Koraguchi, T.; Shimizu, T. J. Org. Chem. 1991, 56,
1613. g) Kim, S.; Lee, S.; Koh, J. S. J. Am. Chem. Soc. 1991, 113,
5106.
reacted with SmI in the presence of HMPA to give the coupled diol
2
product, and no reaction occurred in the absence of HMPA. The precise
role of HMPA was not well understood, however, HMPA molecules may
induce the stronger electron donation effect of samarium ion to generate
2.
3.
4.
a) Dickinson, J. M.; Murphy, J. A.; Patterson, C. W.; Wooster, N.
F. J. Chem. Soc. Perkin Trans. 1. 1990, 1179. b) Feldman, K. S.;
Fisher, T. E. Tetrahedron Lett. 1989, 30, 2969. c) Stogryn, E. L.;
Gianni, M. H. Tetrahedron Lett. 1970, 3025.
16
the cleavage of O - C2 bond.
The mechanism for formation of allylic alcohols is well documented in
reference 9. The mechanism for formation of cyclopropanol is not clear.
It appears to be initiated to form a diradical intermediate following by
cyclopropanation (Figure 1).
a) Pasto, D. J.; Coltard, F.; Picconatto, C. J. Org. Chem. 1994, 59,
7172. b) Sarandeses, L. A.; Luche, J. L. J. Org. Chem. 1992, 57,
7172. c) Barton, D. H. R.; Motherwell, R. S. H.; Motherwell, W.
B. J. Chem. Soc. Perkin Trans. 1. 1981, 2363.
a) Matsukawa, M.; Tabuchi, T.; Inanaga, J.; Mamaguchi, M.
Chem. Lett. 1987, 2101. b) Girard, P.; Namy, J. L.; Kagan, H. B. J.
Am. Chem. Soc. 1980, 102, 2693.
5.
6.
Prandi, J.; Namy, J. L.; Menoret, G.; Kagan, H. B. J. Organomet.
Chem. 1985, 285, 449.
a) Otsubo, K.; Inanaga, J.; Yamaguchi, M Tetrahedron Lett. 1987,
28, 4437. b) Molander, G. A.; La Belle, B. E.; Hahn, G. J. Org.
Chem. 1986, 51, 5259. c) Molander, G. A.; Hahn, G. J. Org.
Chem. 1986, 51, 2596. d) Inanaga, J. Rev. Heteroatom Chem.
1990, 3, 75.
7.
8.
Weghe, P. V.; Collin, J. Tetrahedron Lett. 1995, 36, 1649.
a) Murphy, J. A.; Patterson, C. W. J. Chem. Soc. Perkin Trans. 1.
1993, 405. b) Sarandess, L. A.; Mourino, A.; Luche, J. L. J. Chem.
Soc. Chem. Commun. 1991, 818. c) Johns, A.; Murphy, J. A.;
Patterson, C. W.; Wooster, N. F. J. Chem. Soc. Chem. Commun.
1987, 1238. d) Cook, M.; Hares, O.; Johns, A; Murphy, J. A.;
Patterson, C. W. J. Chem. Soc. Chem. Commun. 1986, 1419.
A
possibility of the debrominated radical rearrangement to the
cyclopropane alkoxy radical can be excluded because the aryl
substituted α- alkyl radical intermediate involves C2 - C3 bond cleavage
predominantly to give a vinyl ether product;
vinyl ether could not be observed. Studies on mechanism and scope are
under progress.
1b, 2, 8a, 8c, 8d
formation of
9.
Hasegawa, E.; Takahashi, M.; Horaguchi, T. Tetrahedron Lett.
1995, 36, 5215.
A typical experimental procedure : To a well-dried and Ar-exchanged
one-neck round flask was placed α-bromo phenyl epoxide (214 mg, 1.0
10. a) Werstiuk, N. H. Tetrahedron 1983, 39, 205. b) Gibson, D. H.;
Depuy, C. H. Chem. Rev. 1974, 74, 605.
mmol), HMPA (840 µl, 3.0 mmol), and THF (10 ml). To the solution
o
cooled to -78 C by dry ice-acetone system was added SmI (20 ml of
2
0.1 M THF solution). After a few minutes, the reaction mixture was
11. a) Sato, T.; Kikuchi, T.; Tsujita, H.; Kaetsu, A.; Sootome, N.;
Nishida, K.; Tachibana, K.; Murayama, E. Tetrahedron Lett. 1991,
47, 3281. b) Takeda, K.; Nakatani, J.; Nakamura, H.; Sako, K.;
Yoshii, E.; Yamaguchi, K. Synlett. 1993, 841. c) Lee, J.; Kim, H.;
Cha, J. K. J. Am. Chem. Soc. 1996, 118, 4198. d) Imai, T.; Mineta,
H.; Nishida, S. J. Org. Chem. 1990, 55, 4986.
quenched with saturated NH Cl and 1N HCl solution. The organic layer
4
was extracted twice with ether (20 ml x 2), once with CH Cl (20 ml),
2
2
and dried over MgSO . Evaporation of solvent afforded crude product
4
which was purified with flash column chromatography (silica gel : 230 -
400 mesh, eluent ; AcOEt : n-hexane = 1: 3), to give 2-phenyl-1-
1
13
cyclopropanol (93 mg, 75%), which was identified by H NMR,
C
12. a) Imamoto, T.; Takeyama, T.; Koto, H. Tetrahedron Lett. 1986,
27, 3243. b) Imamoto, T.; Takiyama, N. Tetrahedron Lett. 1987,
28, 1307.
NMR, and Mass spectroscopy (reference 15).
Acknowledgment This paper was supported (in part) by NON
DIRECTED RESEARCH FUND, Korea Research Foundation and
Center for Biofunctional Molecules of Korea Science and Engineering
Foundation.
13. a) Imamoto, T.; Kamiya, Y.; Hatajima, T.; Takahashi, H.
Tetrahedron Lett. 1989, 37, 5149. b) Fedel, A. Tetrahedron
Asymmetry 1994. 5(4), 531.
14. Kim, Y. H.; and Lee, I. S. Heteroatom Chem. 1992. 3, 509.
13
1
15. The cyclopropanol (2, R = Ph) was confirmed by H NMR,
C
δ
1
References
NMR, IR, and Mass spectroscopy. H NMR (200 MHz, CDCl )
3
0.9 - 1.07 (q, 1H), 1.20 - 1.30 (m, 1H), 2.4 - 2.13 (dt, J = 2.48 Hz
1.
a) Ziegler, F. E.; Petersen, A. K. J. Org. Chem. 1994, 59, 2707. b)
J. A. Murphy, J. A.; Patterson, C. W. Tetrahedron Lett. 1993, 34,
867. c) Rawal, V. H.; Iwasa, S. Tetrahedron Lett. 1992, 33, 4687.
d) Rawal, V. H.; Krishnamurthy, V. Tetrahedron Lett. 1992, 33,
3439. e) Hasegawa, E.; Ishiyama, K.; Kato, T.; Haraguchi, T.;
Shimizu, T. J. Org. Chem. 1992, 57, 5352. f) Hasegawa, E.;
(d), 1H), 3.03 (br, 1H, -OH), 3.56 - 3.62 (m, 1H), 6.97 - 7.37 (5H,
13
Ph) ; C NMR (50 MHz, CDCl ) δ 141.10, 128.26, 125.70,
3
-1
125.65, 55.24, 25.32, 17.67 ; IR (NaCl) 3336.36 cm (-OH) ;
Mass M/e 134, 117, 78.
16. Inanaga, J.; Ishikawa, M.; Yamaguchi, M. Chem. Lett. 1987, 1485.