1632
F. Ma´rquez et al. / Tetrahedron: Asymmetry 12 (2001) 1625–1634
NMR: l 21.3, 34.3, 69.6, 73.3, 74.5, 122.5, 124.8, 127.7,
128.3, 129.9, 137.9, 138.0, 141.6, 152.1; EIHRMS (mix-
ture of diastereomers) calcd for C19H23O3S [M++1]:
331.136792; found: 331.136779.
(1H), 3.90 (1H), 5.71 (1H), 6.04 (1H), 7.28 (2H), 7.45
(2H); 13C NMR: l 21.4, 25.7, 32.4, 35.0, 78.8, 122.4,
124.7, 129.9, 138.2, 141.5, 153.7; IR (film): 3402, 2954,
2869, 1596, 1492, 1479, 1363, 1081, 1031, 1014 cm−1;
[h]D=−19.75 (c 0.80, acetone); mp 70–72°C.
Compound 3j (major (R,RS) diastereomer): 1H NMR: l
2.39 (3H), 2.40–2.50 (1H), 2.51–2.58 (1H), 4.53 (1H),
4.84 (1H), 5.33 (1H), 5.91 (1H), 6.91–6.99 (2H), 7.14–
7.20 (2H), 7.28 (2H), 7.45 (2H); 13C NMR: l 21.4, 39.1,
70.3, 114.8, 124.6, 124.8, 127.3, 130.0, 133.7, 138.9,
141.7, 149.8, 161.8;
Compound 3f (major (R,RS) diastereomer): 1H NMR: l
2.38 (3H), 2.38–2.45 (1H), 2.48–2.55 (1H), 3.75 (3H),
4.05 (1H), 4.77 (1H), 5.32 (1H), 5.93 (1H), 6.80 (2H),
7.12 (2H), 7.26 (2H), 7.45 (2H); 13C NMR: l 21.5, 38.4,
55.2, 71.9, 113.7, 125.9, 126.8, 127.1, 130.3, 133.3,
133.9, 143.0, 145.9, 159.0; IR (film): 3459, 3033, 2956,
2234, 1612, 1514, 1492, 1249, 1178, 1033 cm−1.
1
Compound 3j (minor (S,RS) diastereomer): H NMR: l
2.37 (3H), 4.53 (1H), 4.58–4.63 (1H), 5.77 (1H), 6.09
(1H), 6.91–6.99 (2H), 7.14–7.20 (2H), 7.28 (2H), 7.48
(2H); 13C NMR: l 21.4, 40.6, 72.8, 114.8, 124.7, 125.3,
Compound 3f (minor (S,RS) diastereomer): 1H NMR: l
2.32–2.36 (2H), 2.37 (3H), 3.74 (3H), 4.57 (1H), 5.75
(1H), 6.08 (1H), 7.2 (2H); 13C NMR: l 21.5, 37.1, 55.2,
72.9, 113.9, 125.7, 126.8, 127.5, 130.3, 133.2, 133.8,
129.7,
133.6,
141.7;
EIHRMS
(mixture
of
diastereomers) calcd for C17H15FOS [M+−18]:
143.1,
146.3,
159.2;
EIHRMS
(mixture
of
286.082766; found: 286.082711.
diastereomers) calcd for C18H18O2S (M+−18):
1
298.102752; found: 298.102758.
3k (major (R,RS) diastereomer): H NMR: l 2.39 (3H),
2.46–2.52 (1H), 2.51–2.58 (1H), 4.93 (2H), 5.27 (1H),
5.89 (1H), 7.27–7.30 (2H), 7.32–7.35 (2H), 7.42–7.45
(2H), 7.51–7.53 (2H); 13C NMR: l 21.3, 39.0, 70.3,
124.7, 125.0, 125.3, 126.1, 129.6, 130.0, 137.4, 141.8,
147.3, 149.6.
1
Compound 3g (major (R,RS) diastereomer): H NMR:
l 2.39 (3H), 2.55 (1H), 2.70 (1H), 4.47 (1H), 4.82 (1H),
5.42 (1H), 5.96 (1H), 6.22 (1H), 6.27 (1H), 7.29 (3H),
7.46 (2H); 13C NMR: l 21.3, 36.2, 65.7, 106.5, 110.2,
124.6, 124.8, 130.0, 137.7, 141.4, 141.7, 150.0, 155.8.
1
Compound 3k (minor (S,RS) diastereomer): H NMR:
1
Compound 3g (minor (S,RS) diastereomer): H NMR:
l 2.37 (3H), 4.67 (1H), 5.1 (1H), 5.81 (1H), 6.11 (1H);
13C NMR: l 21.3, 40.5, 72.9, 124.6, 125.2, 125.3, 126.0,
130.0, 137.5, 149.7.
l 2.37 (3H), 2.44–2.62 (2H), 4.47 (1H), 4.64 (1H), 5.77
(1H), 5.09 (1H), 6.20 (1H), 7.29 (3H), 7.46 (2H); 13C
NMR: l 21.3, 36.7, 67.3, 105.9, 110.1, 123.5, 124.8,
130.0, 137.7, 141.4, 141.7, 151.6, 155.6; EIHRMS (mix-
ture of diastereomers) calcd for C15H15O2S [(M+1)+−
18]: 259.079277; found: 259.079223.
Compound 4 (major diastereomer): 1H NMR (200
MHz, CDCl3): l 2.2–2.6 (2H), 4.77 (1H), 5.3 (1H), 5.89
(1H), 7.05–7.6 (10H); 13C NMR (50.3 MHz, CDCl3): l
38.8, 71.1, 124.1, 124.9, 125.6, 127.1, 128.1, 129.2,
131.1, 141.4, 143.1, 150.0.
1
Compound 3h (major (R,RS) diastereomer): H NMR:
l 2.38 (3H), 2.45–2.52 (1H), 2.48–2.55 (1H), 4.89 (1H),
5.27 (1H), 5.92 (1H), 7.18–7.21 (1H), 7.28 (2H), 7.44
(2H), 7.62 (1H), 8.4 (2H); 13C NMR: l 21.4, 39.0, 68.7,
123.2, 124.7, 125.1, 130.0, 133.9, 137.5, 138.9, 141.8,
147.3, 148.2, 149.7.
Compound 4 (minor diastereomer): 1H NMR (200
MHz, CDCl3): l 2.2–2.6 (2H), 4.51–4.59 (1H), 5.71
(1H), 6.02 (1H), 7.05–7.60 (10H); 13C NMR (50.3 MHz,
CDCl3): l 40.1, 71.1, 123.5, 124.7, 125.6, 127.4, 128.3,
143.8, 151.8. Elemental analysis (mixture of
diastereomers) calcd for C16H16O2S: C, 70.59%; H,
5.88%; S, 11.76%; found: C, 70.31%; H, 6.01%; S,
11.56%.
1
Compound 3h (minor (S,RS) diastereomer): H NMR:
l 2.31–2.41 (2H), 2.36 (3H), 4.65 (1H), 5.81 (1H), 6.11
(1H), 7.18–7.21 (1H), 7.28 (2H), 7.44 (2H), 7.62 (1H),
8.4 (2H); 13C NMR: l 21.4, 40.5, 71.1, 123.4, 124.6,
125.1, 130.1, 133.7, 137.5, 139.5, 141.8, 147.4, 148.5,
151.6; EIHRMS (mixture of diastereomers) calcd for
C16H16ONS (M+−17): 270.095262; found: 270.095283.
4.8. Addition of methylamine to 3h
A solution of 3h (6:1 mixture of diastereomers, 0.40 g,
1.45 mmol) in MeOH (4 mL) was treated with 40%
aqueous methylamine (3.5 mL) and the resulting mix-
ture stirred at rt for 12 h. The reaction mixture was
then evaporated to dryness and the residue was taken
up in CH2Cl2 and dried over anhydrous MgSO4 to
afford 3h as a mixture of diastereomers (0.40 g, 90%).
Spectroscopic data for the major diastereomer.
Compound 3i (major (R,RS) diastereomer): 1H NMR: l
2.24–2.31 (1H), 2.32–2.38 (1H), 2.38 (3H), 3.30–3.35
(1H), 3.34–3.39 (1H), 3.65 (1H), 3.88 (1H), 4.47 (2H),
5.73 (1H), 6.09 (1H), 7.26–7.32 (7H), 7.45 (2H); 13C
NMR: l 21.3, 33.0, 67.3, 72.5, 73.2, 122.9, 124.9, 127.6,
127.7, 128.4, 129.9, 137.8, 138.1, 141.6, 150.7.
1
Compound 3i (minor (S,RS) diastereomer): H NMR: l
IR (film): 3299, 2937, 2862, 1594, 1577, 1492, 1474,
1425, 1083, 1027, 1014 cm−1; 1H NMR: l 2.02–2.23
(2H), 2.37–4.45 (6H), 2.48–2.60 (1H), 2.71 (1H), 3.18
(1H), 4.96 (1H), 7.09–7.33 (5H), 7.38–7.69 (2H), 8.40–
2.06–2.14 (1H), 2.38 (3H), 2.38–2.45 (1H), 3.29–3.34
(1H), 3.43–3.48 (1H), 3.72 (1H), 4.07 (1H), 4.49 (2H),
5.75 (1H), 6.06 (1H), 7.26–7.32 (7H), 7.45 (2H); 13C