G. Signore et al. / Tetrahedron 63 (2007) 177–182
181
I%): 250 (Mꢃ+, 4), 234 (30), 202 (56), 163 (29), 131 (100),
124 (49), 118 (51), 105 (18), 91 (36), 77 (9); H NMR:
CH2CH3); 13C NMR: 141.6, 141.1, 140.7, 139.5, 136.0,
130.3, 128.8, 128.7, 126.5, 125.0, 34.6, 33.8, 21.7; Anal.
Calcd for C17H18OS: C, 75.52; H, 6.72; S, 11.84%. Found:
C, 75.42; H, 6.67; S, 11.93%.
1
7.54–7.46 (2H, m, o-Ar), 7.35–7.26 (2H, m, m-Ar), 6.59
(1H, dt, J 15.4 Hz, J0 7.0 Hz, SOCHCH), 6.20 (1H, dt, J
15.4 Hz, J0 1.4 Hz, SOCHCH), 2.40 (3H, s, ArCH3), 2.21
(2H, dtd, J 6.2 Hz, J0 7.0 Hz, J00 1.4 Hz, CHCH2), 1.50–
1.20 (8H, m, (CH2)4CH3), 0.86 (3H, J 6.6 Hz, CH2CH3);
13C NMR: 141.5, 140.9, 134.8, 129.8, 124.4, 31.8, 31.3,
28.5, 27.9, 22.4, 21.2, 13.9; Anal. Calcd for C15H22OS: C,
71.96; H, 8.86; S, 12.78%. Found: C, 71.87; H, 8.73; S,
12.91%.
2.1.4.7. (E) Methyl hex-1-enyl sulfoxide.18 Ethyl Ace-
tate 100%; 35%; yellowish oil; Rf (20% Petroleum ether/
Ethyl Acetate) 0.15; GC–MS (m/z, I%): 146 (Mꢃ+, 49), 129
1
(11), 117 (12), 103 (10), 81 (51), 55 (100), 41 (72); H
NMR: 6.49 (1H, dt, J 15.0 Hz, J0 6.6 Hz, SOCHCH), 6.27
(1H, dt, J 15.0 Hz, J0 1.5 Hz, SOCHCH), 2.60 (3H, s,
SOCH3), 2.24 (2H, dtd, J 7.0 Hz, J0 6.4 Hz, J00 1.5 Hz,
CHCH2), 1.55–1.25 (4H, m, CH2CH2CH3), 0.91 (3H, t,
J 7.0 Hz, CH2CH3); 13C NMR: 141.2, 134.2, 41.0, 31.9,
30.4, 22.4, 14.0; Anal. Calcd for C7H14OS: C, 57.50; H,
9.66; S, 21.89%. Found: C, 57.59; H, 9.74; S, 21.84%.
2.1.4.3. (E) 40-Methylphenyl 2-cyclohexylethenyl sulf-
oxide.16 Petroleum ether/Ethyl Acetate 80/20; 92%; yellow-
ish oil; Rf (20% Petroleum ether/Ethyl Acetate) 0.19; GC–
MS (m/z, I%): 234 (Mꢃ+, 5), 219 (18), 218 (100), 186 (18),
1
136 (36), 109 (71), 67 (63); H NMR: 7.53–7.46 (2H, m,
o-Ar), 7.33–7.27 (2H, m, m-Ar), 6.56 (1H, dd, J 15.0 Hz,
J0 6.6 Hz, SOCHCH), 6.15 (1H, dd, J 15.0 Hz, J0 1.1 Hz,
SOCHCH), 2.40 (3H, s, ArCH3), 2.20–2.10 (1H, m,
CH(CH2)2), 1.90–1.60 (5H, m, CHcycle), 1.40–1.10 (5H, m,
CHcycle); 13C NMR: 146.0, 141.5, 141.4, 133.3, 130.2,
124.8, 40.5, 37.8, 32.0, 31.9, 26.0, 25.9, 21.6; Anal. Calcd
for C15H20OS: C, 77.54; H, 8.12; S, 12.89%. Found: C,
77.45; H, 8.07; S, 13.01%.
2.1.5. NMR of reaction intermediates. All NMR spectra
were recorded on a Varian Infinity 300 spectrometer in
C6D6 solution, using the residual signal of solvent (set ex-
actly at 2134.2 Hz) as reference, and are expressed in Hertz.
1
2.1.5.1. (E) Di (iso-butyl) hex-1-enyl aluminum. H
NMR: 2242 (1H, dt, Jd 20.0 Hz, Jt 6.0 Hz, Al–CH]CH),
1770 (1H, dt, Jd 20.0 Hz, Jt 1.5 Hz, Al–CH]CH), 629.0
(2H, m, CH]CH–CH2–), 601.0 (2H, m, CH2CH(CH3)2),
390.0–345.0 (4H, m, ]CH–CH2–CH2–CH2–), 330.3
(12H, s, CH(CH3)2), 227.0 (3H, t, J 7.0 Hz, CH2–CH3),
111.0 (4H, d, J 7.0 Hz, Al–(CH2CH–)2); 13C NMR: 186.2,
126.3, 40.3, 29.4, 28.3 (2C), 26.8, 22.4, 13.7.
2.1.4.4. (E) 40-Methylphenyl 3,3-dimethyl-but-1-enyl
sulfoxide.17 Petroleum ether/Ethyl Acetate 80/20; 89%; yel-
lowish oil; Rf (20% Petroleum ether/Ethyl Acetate) 0.22;
GC–MS (m/z, I%): 222 (Mꢃ+, 2), 206 (6), 191 (11), 174
(53), 159 (100), 137 (17), 123 (26), 91 (25), 77 (8), 65
1
(14), 57 (16); H NMR: 7.52–7.42 (2H, m, o-Ar), 7.32–
2.1.5.2. Pyridine. 1H NMR: 2543 (2H, m, a-CH), 2101
(1H, tt, J1 7.0 Hz, J2 2.0 Hz, g-CH), 2002 (2H, m, b-CH);
13C NMR: 150.1, 135.2, 123.4.
7.23 (2H, m, m-Ar), 6.60 (1H, J 15.4 Hz, SOCHCH), 6.11
(1H, d, J 15.4 Hz, SOCHCH), 2.49 (3H, s, ArCH3), 1.16
(9H, s, C(CH3)3); 13C NMR: 151.0, 141.5, 141.4, 131.3,
130.2, 124.9, 34.4, 29.0, 21.6; Anal. Calcd for C13H18OS:
C, 70.24; H, 8.17; S, 14.13%. Found: C, 70.20; H, 8.07; S,
14.20%.
2.1.5.3. Tosyl chloride. 1H NMR: 2258 (2H, d, J 8.0 Hz,
a-CH), 1936 (2H, d, J 8.0 Hz, b-CH), 503 (3H, s, –CH3); 13
NMR: 146.1, 142.0, 129.9, 126.9, 21.0.
C
2.1.4.5. (E) 40-Biphenyl hex-1-enyl sulfoxide. Petro-
leum ether/Ethyl Acetate 80/20; 70%; yellowish oil; Rf
(20% Petroleum ether/Ethyl Acetate) 0.18; GC–MS (m/z,
I%): 284 (Mꢃ+, 3), 268 (46), 236 (100), 225 (15), 193 (99),
185 (62), 178 (40), 165 (23), 152 (71), 141 (14), 115 (16),
2.1.5.4. Tosyl chloride–pyridine complex. 1H NMR:
2538 (2H, m, a-CH), 2263 (2H, d, J 8.0 Hz, a-CH), 2099
(1H, tt, J1 7.0 Hz, J2 2.0 Hz, g-CH), 2000 (2H, m, b-CH),
1959 (2H, d, J 8.0 Hz, b-CH), 521 (3H, s, –CH3); 13C
NMR: 150.0, 146.4, 141.9, 135.3, 130.0, 126.9, 123.5, 21.1.
1
77 (7), 55 (12), 41 (16); H NMR: 7.90–7.65 (5H, m, Ph),
7.60–7.45 (4H, m, SOAr), 6.74 (1H, dt, J 150.4 Hz, J0
6.6 Hz, SOCHCH), 6.36 (1H, dt, J 15.4 Hz, J 1.4 Hz,
SOCHCH), 2.34 (2H, dtd, J 6.6 Hz, J0 6.0 Hz, J00 1.4 Hz,
CHCH2), 1.60–1.30 (4H, m, CH2CH2CH3), 0.99 (3H, t,
J 6.6 Hz, CH2CH3); 13C NMR: 144.2, 143.0, 142.1, 140.0,
134.9, 129.2, 128.4, 128.3, 127.5, 125.3, 32.0, 30.4, 22.4,
14.1; Anal. Calcd for C18H20OS: C, 76.01; H, 7.10; S,
11.25%. Found: C, 76.23; H, 7.01; S, 11.20%.
2.1.5.5. (E) Di (iso-butyl) hex-1-enyl aluminum pyri-
dine complex. H NMR: 2513 (2H, m, a-CH), 2038 (1H,
1
tt, J1 7.0 Hz, J2 2.0 Hz, g-CH), 1940 (2H, m, b-CH), 1935
(1H, dt, Jd 20.0 Hz, Jt 6.0 Hz, Al–CH]CH), 1895 (1H, dt,
Jd 20.0 Hz, Jt 1.5 Hz, Al–CH]CH), 708 (2H, m,
CH]CH–CH2–), 646 (2H, m, CH2CH(CH3)2), 480–405
(4H, m, ]CH–CH2–CH2–CH2), 364 (12H, s, CH(CH3)2),
269 (3H, t, J 7.0 Hz, CH2–CH3), 126 (4H, d, J 7.0 Hz,
Al–(CH2CH–)2); 13C NMR: 149.2, 148.7, 137.4, 124.1,
124.0, 39.6, 32.0, 28.7 (2C), 27.3, 22.7, 14.2.
2.1.4.6. (E) 40-Methylphenyl 4-phenyl but-1-enyl sulf-
oxide.17 Petroleum ether/Ethyl Acetate 80/20; 88%; yellow-
ish oil; Rf (20% Petroleum ether/Ethyl Acetate) 0.18; GC–
MS (m/z, I%): 270 (Mꢃ+, 1), 254 (5), 222 (17), 163 (21),
2.1.5.6. (E) Di (iso-butyl) hex-1-enyl aluminum pyridi-
nate–tosyl chloride complex. 1H NMR: 2514 (m, 2H,
a-CH), 2263 (d, J 8.0 Hz, 2H, a-CH), 2061 (tt, J1 7.0 Hz,
J2 2.0 Hz, 1H, g-CH), 1959 (d, J 8.0 Hz, 2H, b-CH), 1950
(m, 2H, b-CH), 1929 (dt, Jd 20.0 Hz, Jt 6.0 Hz, 1H,
Al–CH]CH), 1884 (dt, Jd 20.0 Hz, Jt 1.5 Hz, 1H,
Al–CH]CH), 699 (m, 2H, CH]CH–CH2–), 636 (m, 2H,
1
131 (110), 123 (14), 91 (73), 77 (10), 65 (16); H NMR:
7.55–7.20 (9H, m, Ph+SOAr), 6.69 (1H, dt, J 15.4 Hz,
J0 7.4 Hz, SOCHCH), 6.28 (dt, J 15.4 Hz, J0 1 Hz,
SOCHCH), 2.87 (2H, t, J 7.2 Hz, SOCH2), 2.63 (2H, dtd,
J 7.0 Hz, J0 7.4 Hz, J00 1, 2.0 Hz, CH2Ph), 2.49 (3H, s,