902
J. Lin et al.
LETTER
(S,S)-( )-3f: yellow liquid, Rf = 0.30 (hexane–ether = 2:1);
1H NMR (200 MHz, CDCl3) 0.83 (t, J = 6.4 Hz, 3 H), 1.24
(t, J = 7.6 Hz, 3 H), 1.18–1.76 (m, 8 H), 2.66 (q, J = 7.6 Hz,
2 H), 3.82 (s, 3 H), 3.91 (s, 1 H), 4.68 (dd, J = 1.8 Hz and
10.8 Hz, 1 H), 7.21 (d, J = 8.4 Hz, 2 H), 7.57 (d, J = 8.4 Hz,
2 H); 13C NMR (200 MHz, CDCl3) 13.89, 15.28, 22.38,
26.58, 28.37, 30.51, 30.87, 53.53, 68.30, 81.23, 125.85,
127.98, 134.97, 144.34, 173.58; IR(neat): 3514, 2958, 2932,
2864, 1742, 1512, 1437, 1257, 1147, 756 cm–1; Anal. Calcd
for C17H25ClO3: C, 65.27; H, 8.05; Found: C, 65.51; H, 8.22.
(S,R)-( )-3f: yellow liquid, Rf = 0.23 (hexane–ether = 2.1);
1H NMR(200 MHz, CDCl3) 0.90 (t, J = 6.4 Hz, 3 H), 1.24
(t, J = 7.6 Hz, 3 H), 1.20–2.10 (m, 8 H), 2.66 (q, J = 7.6 Hz,
2 H), 3.73 (s, 1 H), 3.81 (s, 3 H), 4.61 (dd, J = 1.6 Hz and
10.8 Hz, 1 H), 7.21 (d, J = 8.4 Hz, 2 H), 7.53 (d, J = 8.4 Hz,
2 H); 13C NMR (200 MHz, CDCl3) 13.97, 15.22, 22.42,
26.57, 28.37, 31.05, 33.11, 53.58, 67.65, 81.25, 125.70,
127.83, 136.63, 144.32, 173.10; IR(neat): 3512, 2962, 2934,
2864, 1734, 1514, 1458, 1253, 1143, 835, 665 cm–1; Anal.
Calcd for C17H25ClO3: C, 65.27; H, 8.05; Found: C, 65.51;
H, 8.22.
Acknowledgement
We are grateful to SC-NMR laboratory of Okayama University for
the measurement of NMR spectra.
References
(1) Friedel–Crafts and Related Reaction; Olah, G. A., Ed.;
Interscience: New York, 1964.
(2) (a) Hata, S.; Matsuda, H.; Mastuda, S. Kogyo Kagaku Zasshi
1967, 70(12), 2291. (b) Nakamoto, Y.; Nakajima, T.; Suga,
S. Kogyo Kagaku Zasshi 1969, 72(12), 2594. (c) Nakajima,
T.; Nakamoto, Y.; Suga, S. Bull. Chem. Soc. Jpn. 1975,
48(3), 960. (d) Inoue, M.; Chano, K.; Itoh, O.; Sugita, T.;
Ichikawa, K. Bull. Chem. Soc. Jpn. 1980, 53, 458.
(3) Juy, M.; Combert, J. C.; Coutrot, P. C. R. Hebd. Seances
Acad. Sci., Ser. C 1974, 279, 469.
(4) (a) Ubaidullaev, K. A.; Shakairov, R.; Yunosov, S. Y. Khim.
Prir. Soedin. 1976, 12, 553. (b) Hasse, B. R.; John, K. M. J.
Nat. Prod. 1997, 60, 1152.
(5) Typical procedure for ( )-2-hydroxy-2-(p-ethylphenyl)-3-
chlorooctanoate(3f): To a stirred solution of aluminium
chloride (430 mg, 3 mmol) in CH2Cl2 (4 mL) was added the
solution of methyl 2-chloro-2,3-epoxyoctanoate (206 mg, 1
mmol) and ethylbenzene (319 mg, 3 mmol) in CH2Cl2 (2
mL) at room temperature. The mixture was stirred for 50
minutes, then reaction was stopped by pouring the ice (10
mL), and the aqueous layer was extracted with EtOAc. The
combined extract was washed with saturated NaHCO3
solution and brine, then dried over MgSO4. Removal of the
solvent gave 232 mg of a clean oil, which was purified by
column chromatography (hexane–ether = 160:1) to give 161
mg (51.5%) of (S,S)-( )-3f and 38 mg (12.1%) of (S,R)-( )-
3f.
(6) X-ray crystallographic data of syn-3d: data collection,
solution, and refinement.
Chemical formula: C14H19O3Cl; F. W. = 270.76; crystal size:
0.50 0.25 0.43 mm3; crystal system: triclinic; lattice
parameters: a = 10.495(3), b = 11.755(3), c = 6.608(2) Å,
= 100.36(2), = 107.25(3), = 69.213(18)º, V = 725.4(4)
Å3; space group: P (#2); Z = 2; Dcalc = 1.240 g/cm3; F(000)
= 288; (Mo K ) = 0.26 mm–1; diffractometer: Rigku
AFC5R; T: 25 ºC; no. of reflections measured: total 3880,
unique 3334; structure solution: direct methods (SIR92);
refinement: full-matrix least-squares on F2; function mini-
mized: w (Fo2 – Fc2)2; least squares weights: 1/ 2(Fo) =
4Fo2/ 2 (Fo2); no. obsd [I > 0.5 (I)]: 2886; no. variables:
240; residuals R1, wR2: 0.063, 0.099; goodness of fit
indicator: 1.94; max
/
min: 0.23 / – 0.28 e / Å3.
Synlett 2002, No. 6, 899–902 ISSN 0936-5214 © Thieme Stuttgart · New York