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H. Miyaoka et al. / Tetrahedron 56 (2000) 8077±8081
General procedure for the synthesis of cycloalkane 2a±f.
To a solution of allyl phenyl sulfone (1.35 mmol) in THF
(5.0 mL) was added BuLi (1.3 mmol, hexane solution) at
2788C. The mixture was stirred for 30 min at same
temperature. A solution of epoxide 1a±f (0.565 mmol) in
THF (0.6 mL) was added to the resultant mixture and the
reaction mixture was warmed to rt over 5 h and stirred for
2 h at ambient temperature. After the usual work-up,
chromatographic puri®cation on silica gel gave cycloalkane
2a±f in 47±96% yield. The ratio of diastereomers was
dd, J17.3, 1.0 Hz), 5.44 (1H, d, J10.4 Hz), 6.14 (1H, dd,
J17.3, 10.4 Hz), 7.51 (2H, m), 7.62 (1H, m), 7.78 (2H, m);
13C NMR (75 MHz, CDCl3) d ppm: 12.1, 30.3, 30.4, 34.2,
48.2, 69.2, 125.5, 128.7, 128.7, 129.0, 133.4, 137.8; EIMS
(m/z): 266 (M1), 251, 195, 124, 72; HREIMS: Calcd for
C14H18O3S (M1) 266.0977: Found: 266.0975.
2c minor. Colorless oil. IR (neat) 3467, 2979, 1634, 1286,
1142 cm21; 1H NMR (300 MHz, CDCl3) d ppm: 1.37 (3H,
s), 1.44 (1H, dd, J9.6, 5.6 Hz), 1.64 (3H, s), 1.65 (1H, dd,
J9.6, 8.8 Hz), 2.07 (1H, dd, J8.8, 5.6 Hz), 4.84 (1H, d,
J17.0 Hz), 5.12 (1H, d, J10.3 Hz), 6.19 (1H, dd, J17.0,
10.3 Hz), 7.51 (2H, m), 7.62 (1H, m), 7.82 (2H, m); 13C
NMR (75 MHz, CDCl3) d ppm: 15.4, 30.6, 31.0, 47.3,
50.8, 67.4, 119.6, 128.8, 133.5, 133.5, 139.0; EIMS (m/z):
266 (M1), 251, 195, 143, 124, 72; HREIMS: Calcd for
C13H15O3S (M12CH3) 251.0742: Found: 251.0738.
1
determined by H NMR analysis.
2a major. Colorless solid. mp 131±1338C; IR (KBr) 3494,
2960, 2932, 2973, 1447, 1306, 1139 cm21 1H NMR
;
(300 MHz, CDCl3) d ppm: 0.88 (3H, t, J7.0 Hz), 1.2±
1.7 (6H, m), 2.22 (1H, m), 3.14 (1H, m), 5.12 (1H, d,
J17.0 Hz), 5.37 (1H, d, J10.4 Hz), 6.00 (1H, dd,
J17.0, 10.4 Hz), 7.52 (2H, m), 7.61 (1H, m), 7.79 (2H,
m); 13C NMR (75 MHz, CDCl3) d ppm: 13.9, 14.1, 18.3,
29.8, 39.6, 48.7, 70.3, 124.4, 128.0, 128.7, 128.8, 133.4,
137.9; EIMS (m/z): 280 (M1), 195, 143, 125, 77; Anal.
Calcd for C15H20O3S: C, 64.26; H, 7.19. Found: C, 64.35;
H, 7.11.
2d. Colorless oil. IR (neat) 3517, 2963, 1634, 1585, 1289,
1140 cm21; 1H NMR (300 MHz, CDCl3) d ppm: 0.96 (3H, t,
J7.4 Hz), 1.28 (1H, m), 1.46 (1H, m), 1.55 (1H, m), 1.99
(2H, m), 2.67 (1H, m), 3.31 (1H, dd, J18.2, 10.1 Hz), 3.46
(1H, ddd, J10.1, 7.5, 3.2 Hz), 5.10 (1H, d, J17.3 Hz),
5.42 (1H, d, J10.7 Hz), 6.20 (1H, dd, J17.3, 10.7 Hz),
7.49 (2H, m), 7.61 (1H, m), 7.74 (2H, m); 13C NMR
(75 MHz, CDCl3) d ppm: 9.3, 18.9, 22.1, 26.2, 45.2, 70.5,
71.4, 121.6, 128.6, 129.5, 133.7, 135.3; EIMS (m/z): 282
(M1), 251, 222, 200, 143, 121, 81; HREIMS: Calcd for
C15H22O3S (M1) 282.1290: Found: 282.1263.
2a minor. Colorless oil. IR (neat) 3471, 2959, 2934, 2873,
1
1634, 1586, 1448, 1307, 1141 cm21; H NMR (300 MHz,
CDCl3) d ppm: 0.96 (3H, t, J7.0 Hz), 1.4±1.7 (5H, m),
1.96 (1H, m), 2.51 (1H, m), 4.38 (1H, m), 4.94 (1H, d, J
17.0 Hz), 5.14 (1H, d, J10.3 Hz), 6.13 (1H, dd, J17.0,
10.3 Hz), 7.53 (2H, m), 7.61 (1H, m), 7.82 (2H, m); 13C
NMR (75 MHz, CDCl3) d ppm: 13.9, 16.8, 18.6, 37.8,
39.9, 49.5, 67.5, 120.2, 128.5, 128.7, 132.7, 133.4, 139.3;
EIMS (m/z): 280 (M1), 195, 143, 125, 91; Anal. Calcd for
C15H20O3S: C, 64.26; H, 7.19. Found: C, 64.05; H, 7.20.
2e. Colorless oil. IR (neat) 3494, 2956, 1633, 1585, 1284,
1161, 1137 cm21; 1H NMR (300 MHz, CDCl3) d ppm: 0.89
(3H, t, J6.7 Hz), 1.2±1.85 (12H, m), 1.92 (1H, m), 2.21
(1H, m), 2.86 (1H, m), 3.54 (1H, m), 4.98 (1H, d, J
17.3 Hz), 5.40 (1H, d, J10.9 Hz), 6.48 (1H, dd, J17.3,
10.9 Hz), 7.49 (2H, m), 7.62 (1H, m), 7.81 (2H, m); 13C
NMR (75 MHz, CDCl3) d ppm: 14.0, 22.4, 22.6, 24.5,
29.5, 32.0, 32.3, 36.0, 51.3, 70.3, 76.9, 121.5, 128.3,
130.5, 131.8, 133.7, 135.2; EIMS (m/z): 336 (M1), 265,
242, 143, 123, 95; HREIMS: Calcd for C14H17O3S
(M12C5H11) 265.0898: Found: 265.0903.
2b major. Colorless solid. mp 94±958C; IR (KBr) 3516,
2959, 2873, 1636, 1448, 1305, 1138 cm21 1H NMR
;
(300 MHz, CDCl3) d ppm: 0.90 (3H, t, J7.2 Hz), 1.05
(1H, t, J6.2 Hz), 1.3±1.65 (4H, m), 1.70 (1H, dd J9.8,
5.7 Hz), 1.84 (1H, br s), 2.23 (1H, m), 3.04 (1H, m), 5.13
(1H, d, J17.1 Hz), 5.39 (1H, d, J10.2 Hz), 6.12 (1H, dd,
J17.1, 10.2 Hz), 7.50 (2H, m), 7.60 (1H, m), 7.82 (2H, m);
13C NMR (75 MHz, CDCl3) d ppm: 13.9, 14.0, 18.5, 30.6,
39.0, 48.3, 70.3, 124.6, 128.0, 128.6, 128.7, 133.2, 137.9;
EIMS (m/z): 280 (M1), 263, 195, 143, 125, 77; Anal. Calcd
for C15H20O3S: C, 64.26; H, 7.19. Found: C, 64.23; H, 7.17.
2f. Colorless oil. IR (neat) 3467, 2937, 1586, 1284, 1147,
1126 cm21; 1H NMR (300 MHz, CDCl3) d ppm: 1.05 (3H, t,
J7.3 Hz), 1.1±2.0 (10H, m), 2.47 (1H, dt, J12.1, 3.6 Hz),
4.40 (1H, br d, J9.4 Hz), 4.98 (1H, d, J17.7 Hz), 5.54
(1H, d, J11.0 Hz), 6.19 (1H, dd, J17.7, 11.0 Hz), 7.49
(2H, m), 7.61 (1H, m), 7.78 (2H, m); 13C NMR (75 MHz,
CDCl3) d ppm: 11.0, 21.8, 24.4, 25.6, 26.8, 30.5, 48.6, 72.1,
72.2, 122.8, 129.1, 130.9, 133.5, 135.3; EIMS (m/z): 279,
200, 143, 108; HREIMS: Calcd for C15H19O3S (M12C2H5)
279.1055: Found: 279.1054.
2b minor. Colorless oil. IR (neat) 3530, 2959, 2871, 1634,
1447, 1288, 1186, 1139 cm21; 1H NMR (300 MHz, CDCl3)
d ppm: 0.95 (3H, t, J7.2 Hz), 1.4±1.7 (6H, m), 1.81 (1H,
dd, J7.7, 5.5 Hz), 2.82 (1H, d, J3.0 Hz), 4.24 (1H, m),
5.04 (1H, d, J17.0 Hz), 5.10 (1H, d, J10.2 Hz), 5.90 (1H,
dd, J17.0, 10.2 Hz), 7.54 (2H, m), 7.63 (1H, m), 7.85 (2H,
m); 13C NMR (75 MHz, CDCl3) d ppm: 14.2, 17.5, 18.9,
38.2, 39.2, 49.3, 69.5, 77.4, 120.7, 128.9, 132.6, 133.6,
139.0; EIMS (m/z): 280 (M1), 263, 195, 143, 125; Anal.
Calcd for C15H20O3S: C, 64.26; H, 7.19. Found: C, 63.97;
H, 7.20.
General procedure for the synthesis of lactone 3a±f. A
cold (2788C) solution of cycloalkane 2a±c major or 2d±f
(0.32 mmol) in CH2Cl2 (2.0 mL) and MeOH (2.0 mL) was
treated with ozone until blue color persisted for more than
4 h. Excess ozone was removed by an argon ¯ow. The
reaction mixture was treated with excess Me2S (9.73
mmol), allowed to warm slowly to rt over 2 h, stirred for
8 h at this temperature and concentrated under reduced
pressure. The residue was diluted with Et2O, washed with
H2O and saturated aqueous NaCl, dried over anhydrous
2c major. Colorless oil. IR (neat) 3359, 2969, 1585, 1283,
1141 cm21; 1H NMR (300 MHz, CDCl3) d ppm: 1.31 (3H,
s), 1.34 (3H, s), 1.49 (1H, dd, J7.4, 5.3 Hz), 1.61 (1H, dd,
J10.3, 5.3 Hz), 2.30 (1H, dd, J10.3, 7.4 Hz), 5.04 (1H,