H. Gu et al. / Tetrahedron Letters 46 (2005) 6449–6451
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3. (a) Mehta, G.; Singh, V. Chem. Rev. 1999, 99, 881, and
references cited therein; (b) Shimada, Y.; Nakamura, M.;
Suzuka, T.; Matsui, J.; Tatsumi, R.; Tsutsumi, K.; Mor-
imoto, T.; Kurosawa, H.; Kakiuchi, K. Tetrahedron Lett.
2003, 44, 1401.
4. Jones, E. R. H.; Eglinton, G.; Whiting, M. C. Organic
Syntheses, Collect.; John Wiley and Sons, Inc.: New York,
1963; Vol. IV, p 755.
tography with n-hexane–EtOAc (4:1, v/v) as the eluent gave
98 mg (98%) 8-chloromethyl-2-hydroxy-11-methylene-tri-
cyclo[5.3.1.0]undecane 14. Oil; 1H NMR (CDCl3) d 4.92
(1H, d, J = 2.4 Hz), 4.72 (1H, d, J = 2.4 Hz), 3.92 (1H, d,
J = 11.2 Hz), 3.74 (1H, d, J = 11.2 Hz), 2.59–2.55 (1H, m),
2.47–2.44 (1H, m), 1.24–2.20 (13H, m); 13C NMR (CDCl3)
d 157.8, 103.7, 85.5, 55.5, 54.0, 47.7, 46.6, 38.9, 34.9, 29.1,
28.1, 26.0, 22.9; MS m/z 226 (M+, 100), 228 (M++2, 33); IR
mmax 1623, 1470, 1411, 1095 (cmÀ1). Elemental analysis
calcd for C13H19ClO: C, 68.86; H, 8.45; Cl, 15.64. Found:
C, 69.03; H, 8.51; Cl, 15.56.
5. Sadhu, K. M.; Matteson, D. S. Tetrahedron Lett. 1986, 27, 795.
6. Typical preparation of chlorohydrin 11 is described as
follows: a solution of fleshly distilled 2-(5-heptynyl) cyclo-
pent-2-enone 10 (0.352 g, 2 mmol) and iodochloromethane
(0.512 g, 3 mmol) in 5 mL ethyl ether and 5 mL dry THF
was cooled to À100 °C under argon. 1.5 mL n-BuLi (2.0 M
in hexane, 3 mmol) was added dropwise over a period of
10 min. The mixture was allowed to set for another 10 min
at À100 °C before quenched with 1 mL water. The mixture
was treated with saturated ammonium chloride and
extracted with ether. Dryness followed by purification via
flash chromatography with n-hexane–EtOAc (4:1, v/v) as
the eluent gave 0.43 g (95%) chlorohydrin 11.
7. Typical preparation of 8-chloromethyl-2-hydroxy-11-meth-
ylene-tricyclo[5.3.1.0]undecane 14 is described as follows:
to a solution of 100 mg chlorohydrin 11 in 2 mL ether,
30 mL trifluoroacetic acid was added at 0 °C with stirring.
The mixture was neutralized with excess cold potassium
carbonate solution within a minute and extracted with
ether. Dryness followed by purification via flash chroma-
8. Typical preparation of 8,11-dimethylene-bicyclo[5.3.1]-
undecan-2-one 17 is described as follows: to a solution of
50 mg tricyclo[5.3.1.0]undecane 14 in 1.5 mL DMF, NaH
(0.3 g) was added with stirring. After about 45 s, the
mixture was neutralized with excess saturated ammonium
chloride and extracted with hexane. Dryness followed by
purification via flash chromatography with n-hexane–
CH2Cl2 (4:1, v/v) as the eluent gave 41 mg (98%) 8,11-
1
dimethylene-bicyclo[5.3.1]undecan-2-one 17. Oil; H NMR
(CDCl3) d 5.12 (1H, d, J = 1.4 Hz), 5.04 (1H, d, J =
1.4 Hz), 4.64 (1H, d, J = 2.0 Hz), 4.56 (1H, d, J = 2.0 Hz),
3.05–3.02 (1H, m), 2.94–2.90 (2H, m), 2.44–2.54 (2H, m),
1.98–2.10 (2H, m), 1.21–1.86 (7H, m); 13C NMR (CDCl3) d
195.9, 151.5, 147.6, 115.5, 107.4, 56.0, 54.5, 39.1, 32.1, 30.9,
29.7, 26.1, 24.2; MS m/z 190 (M+, 100); IR mmax 1711, 1627,
1466 (cmÀ1). Elemental analysis calcd for C13H18O: C,
82.06; H, 9.53. Found: C, 82.17; H, 9.58.