J. L. García Ruano et al.
[a]2D0 =+128.4 (c=0.4 in CHCl3). 1H NMR (300 MHz): d=7.93 (d, J=
8.3 Hz, 1H), 7.52–7.22 (m, 12H), 6.56 (d, J=8.6 Hz, 2H), 5.83 (d, J=
2.5 Hz, 2H), 5.70 (dd, J=8.6, 2.3 Hz, 1H), 4.75 (brs, 1H), 4.13 (d, J=
10.1 Hz, 1H), 3.65 (s, 3H), 3.59 (dq, J=10.1, 6.9 Hz, 1H), 2.34 (s, 3H),
0.64 ppm (d, J=6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3): d=149.5,
145.5, 142.9, 142.1, 141.9, 141.1, 140.5, 132.5, 129.9, 128.3, 127.8 (2C),
127.7, 127.4, 127.1 (2C), 126.9, 125.4, 113.0, 103,5, 98.8, 64.5, 56.5, 55.4,
40.2, 21.2, 19.1 ppm. Elemental analysis calcd (%) for C30H31NO3S: C
74.20, H 6.43, N 2.88, S 6.60; found: C 74.00, H 6.31, N 3.18, S 6.73.
(1R)-N-(2,4,6-Trimethoxyphenyl)-1-(4-chlorophenyl)-2-{2-[(S)-p-tolylsul-
finyl]phenyl}ethylamine (5’’e): This compound was obtained as the major
diastereoisomer by using imine 3’’e and (S)-1 as the starting materials.
Chromatography: n-hexane/AcOEt, 3:1; yield: 72%; yellow oil. [a]D20
=
1
32.4 (c=0.4 in CHCl3). H NMR (300 MHz, CDCl3): d=7.78 (dd, J=3.4,
2.3 Hz, 1H), 7.48–7.43 (m, 3H), 7.33–7.28 (m, 3H), 7.27–7.14 (m, 5H),
6.02 (s, 2H), 4.85 (t, J=7.4 Hz, 1H), 3.72 (s, 3H), 3.65 (s, 6H), 3.31 (dd,
J=7.4, 3.4 Hz ,1H), 3.14 (dd, J=7.4, 3.4 Hz , 1H), 2.34 ppm (s, 3H). 13C
NMR (75 MHz, CDCl3): d=154,8, 152.0, 143.8, 143.3, 142.0, 141.2, 137.9,
130.7, 129.9, 129.8, 128.1, 127.5, 126.9, 125.7, 125.3, 124.9, 118.9, 91.4,
61.6, 55.8, 55.4, 39.9, 21.3 ppm.
A
nyl}propylamine (7’n): This compound was obtained as the major diaste-
reoisomer by using imine 3’n and (S)-2 as the starting materials. Chroma-
tography: n-hexane/AcOEt, 2:1; yield: 66%; brown solid; m.p. 84–868C.
(1R)-N-(2,4,6-Trimethoxyphenyl)-1-(4-methoxyphenyl)-2-{2-[(S)-p-tolyl-
sulfinyl]phenyl}ethylamine (5’’h): This compound was obtained as the
major diastereoisomer by using imine 3’’h and (S)-1 as the starting mate-
rials. Chromatography: n-hexane/AcOEt, 3:1; yield: 76%; yellow solid;
m.p. 135–1378C; [a]2D0 =72.5 (c=1.0 in CHCl3). 1H NMR (300 MHz,
CDCl3): d=7.73 (d, J=6.7 Hz, 1H), 7.40 (d, J=8.1 Hz, 2H), 7.25–7.19
(m, 1H), 7.14–6.97 (m, 4H), 6.66 (t, J=8.5 Hz, 2H), 7.02 (d, J=8.5 Hz,
2H), 5.97 (s, 2H), 4.78 (t, J=7.4 Hz, 1H), 3.65 (s, 3H), 3.63 (s, 6H), 3.60
(s, 3H), 3.25 (dd, J=6.8, 6.7 Hz, 1H), 3.07 (dd, J=7.6, 7.4 Hz, 1H),
2.26 ppm (s, 3H). 13C NMR (75 MHz, CDCl3): d=158.2, 154.6, 152.3,
151.2, 143.5, 141.8, 141.0, 137.9, 135.2, 130.4, 129.7, 127.6, 127.3, 125.6,
124.7, 118.8, 113.2, 91.2, 60.7, 55.6, 55.2, 54.9, 39.7, 21.2 ppm.
1
[a]2D0 =À8.6 (c=0.6 in CHCl3). H NMR (300 MHz, CDCl3): d=7.57 (dd,
J=7.6, 1.6 Hz, 1H), 7.43–7.11 (m, 11H), 6.56 (d, J=8.6 Hz, 1H), 6.10 (d,
J=2.6 Hz, 2H), 5.89 (dd, J=8.6, 2.6 Hz, 1H), 4.75 (brs, 1H), 4.44 (d, J=
5.8 Hz, 1H), 4.00 (dq, J=7.1, 5.8 Hz, 1H), 3.71 (s, 3H), 3.67 (s, 3H), 2.36
(s, 3H), 1.23 ppm (d, J=7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): d=
149.6, 143.8, 142.9, 142.3, 141.4, 141.2, 141.0, 140.8, 131.5, 130.0, 129.7,
129.2, 128.1, 127.5, 126.9, 126.0, 125.4, 125.3, 111.9, 104.4, 99.5, 63.7, 56.5,
55.4, 40.2, 21.2, 18.0 ppm. IR (NaCl): n˜ =3323, 1615, 1596, 1234,
1026 cmÀ1. Elemental analysis calcd (%) for C30H31NO3S: C 74.20, H
6.43, N 2.88, S 6.60; found: C 74.12, H 6.32, N 2.87, S 6.59.
A
(1S,2S/1R,2S)-N-(2,4,6-Trimethoxyphenyl)-1-(4-cyanophenyl)-2-{2-[(S)-p-
tolylsulfinyl]phenyl}propylamine (6’’b/7’’b): These compounds were ob-
tained as an inseparable mixture starting from 3’’b and (S)-2. Chromatog-
raphy: n-hexane/AcOEt, 4:1; yield: 72%. Minor diastereoisomer: 1H
NMR (300 MHz, CDCl3): d=7.48 (d, J=9.2 Hz, 1H), 7.40–7.05 (m, 6H),
7.10–6.95 (m, 3H), 6.90 (d, J=8.2 Hz, 2H), 5.82 (s, 2H), 4.62 (d, J=10.2,
1H), 3.66 (s, 6H), 3.48 (s, 3H), 3.41–3.22 (m, 1H), 2.28 (s, 3H), 0.72 ppm
(d, J=3.9 Hz, 3H). Major diastereoisomer: 1H NMR (300 MHz, CDCl3):
d=7.92 (d, J=8.0 Hz, 1H), 7.42–7.34 (m, 5H), 7.15–6.97 (m, 4H), 6.96
(d, J=8.2 Hz, 2H), 5.93 (s, 2H), 4.90 (d, J=9.21, 1H), 3.82–3.91 (m,
1H), 3.75 (s, 3H), 3.74 (s, 6H), 2.26 (s, 3H), 1.52 ppm (s, J=6.8 Hz, 3H).
nyl}propylamine (6’l): This compound was obtained as the minor diaste-
reoisomer by using imine 3’l and (S)-2 as the starting materials. Chroma-
tography: n-hexane/AcOEt, 1:1; yield: 8%; yellow oil. 1H NMR
(300 MHz, CDCl3): d=7.85 (d, J=9.1 Hz, 1H), 7.48 (d, J=8.3 Hz, 2H),
7.42–7.11 (m, 10H), 6.15 (d, J=3.0 Hz, 1H), 6.13 (d, J=8.6 Hz, 1H), 6.10
(d, J=8.8 Hz, 1H), 4.45 (d, J=7.0 Hz, 1H), 4.00–4.20 (m, 1H), 3.93 (s,
3H), 3.92 (s, 3H), 2.35 (s, 3H), 1.21 ppm (d, J=9.8 Hz, 3H).
(1R,2S)-N-(2,4-Dimethoxyphenyl)-1-phenyl-2-{2-[(S)-p-tolylsulfinyl]phe-
nyl}propylamine (7’l): This compound was obtained as the major diaste-
reoisomer by using imine 3’l and (S)-2 as the starting materials. Chroma-
tography: n-hexane/AcOEt, 1:1; yield: 68%; brown solid; m.p. 81–838C.
A
[a]2D0 =+43.2 (c=0.6 in CHCl3). H NMR (300 MHz, CDCl3): d=7.86 (d,
[(S)-p-tolylsulfinyl]phenyl}propylamine (6’’c): This compound was ob-
tained as the minor diastereoisomer by using imine 3’’c and (S)-2 as the
starting materials. Chromatography: n-hexane/AcOEt, 3:1; yield: 9%;
white solid; m.p. 161–1638C. [a]2D0 =+92.0 (c=1.0 in CHCl3). 1H NMR
(300 MHz, CDCl3): d=7.65 (d, J=6.7 Hz, 1H), 7.48–7.34 (m, 5H), 7.29–
7.26 (m, 2H), 7.16 (t, J=9.1 Hz, 4H), 5.80 (s, 2H), 4.59 (d, J=10.2 Hz,
1H), 3.86 (brs, 1H), 3.74–3.69 (m, 1H), 3.54 (s, 3H), 3.49 (s, 6H), 2.25 (s,
3H), 0.70 ppm (d, J=6.8 Hz, 3H). 13C NMR (75 MHz, CDCl3): d=154.6,
J=9.2 Hz, 1H), 7.57 (d, J=8.3 Hz, 2H), 7.40–7.11 (m, 10H), 6.28 (d, J=
2.5 Hz, 1H), 6.13 (dd, J=8.7, 2.6 Hz, 1H), 6.07 (d, J=8.7 Hz, 1H), 4.42
(brs, 1H), 4.07 (d, J=6.5 Hz, 1H), 4.00 (dq, J=6.9, 6.5 Hz, 1H), 3.63 (s,
3H), 3.59 (s, 3H), 2.34 (s, 3H), 0.98 ppm (d, J=7.1 Hz, 3H). 13C NMR
(75 MHz, CDCl3): d=151.5, 147.7, 144.0, 143.1, 142.4, 141.8, 141.2, 131.7,
131.6, 129.8, 128.2, 127.7, 127.3 (2C), 127.1, 126.3, 125.7, 111.1, 103.5,
99.1, 64.1, 55.5, 55.4, 40.9, 21.3, 19.2 ppm. IR (NaCl): n˜ =3346, 1596,
1518, 1031 cmÀ1. Elemental analysis calcd (%) for C30H31NO3S: C 74.20,
H 6.43, N 2.88, S 6.60; found: C 74.12, H 6.48, N 3.22, S 6.28.
151.4, 147.9, 145.3, 142.6, 141.9, 140.9, 131.7, 129.8, 128.7 (q, JC,F
=
128.7 Hz), 127.7, 127.8, 125.8, 124.7, 124.6, 124.5, 122.4, 119.4, 91.5, 65.4,
55.7, 55.3, 40.1, 21.3, 20.2 ppm.
Products from the reactions of (S)-1 and (S)-2 with N-(2,4,6-trimethoxy-
phenyl)arylideneamines 3’’ (Table 6)
A
[(S)-p-tolylsulfinyl]phenyl}propylamine (7’’c): This compound was ob-
tained as the major diastereoisomer by using imine 3’’c and (S)-2 as the
starting materials. Chromatography: n-hexane/AcOEt, 3:1; yield: 51%;
yellow solid; m.p. 142–1448C. [a]2D0 =101.0 (c=0.9 in CHCl3). 1H NMR
(300 MHz, CDCl3): d=7.67 (d, J=7.7 Hz, 1H), 7.46–7.40 (m, 4H), 7.31–
7.08 (m, 6H), 6.95 (d, J=8.1 Hz, 1H), 5.93 (s, 2H), 4.90 (d, J=9.1 Hz,
1H), 4.01 (brs, 1H), 3.88–3.83 (m, 1H), 3.62 (s, 6H), 3.60 (s, 3H), 2.29 (s,
3H), 1.52 ppm (d, J=6.8 Hz, 3H). 13C NMR (75 MHz, CDCl3): d=154.3,
A
sulfinyl]phenyl}ethylamine (4’’b/5’’b): These compounds were obtained
as an inseparable mixture of diastereoisomers. Chromatography: n-
hexane/AcOEt, 4:1. Yield: 70%; yellow oil. Minor diastereoisomer: 1H
NMR (300 MHz, CDCl3): d=7.62 (d, J=6.7 Hz, 1H), 7.38–7.20 (m, 5H),
6.17–7.10 (m, 6H), 5.93 (s, 2H), 4.85 (t, J=7.2 Hz, 1H), 3.76 (s, 6H), 3.68
(s, 3H), 3.22–3.35 (m, 2H), 2.27 ppm (s, 3H). Major diastereoisomer: 1H
NMR (300 MHz, CDCl3): d=7.88 (d, J=7.4 Hz, 1H), 7.40–7.22 (m, 5H),
6.19–7.10 (m, 6H), 5.01 (s, 1H), 4.96 (dd, J=6.9, 3.0 Hz, 1H), 3.78 (s,
6H), 3.62 (s, 3H), 3.12–3.17 (m, 2H), 2.29 ppm (s, 3H).
151.2, 147.5, 145.0, 142.4, 141.1, 140.3, 129.7, 128.2, 127.9, 127.6 (q, JC,F
=
126.3 Hz), 127.5, 126.9, 125.8, 125.4, 124.3, 124.2, 118.9, 91.5, 64.7, 55.7,
55.3, 41.6, 21.2, 19.9 ppm.
(1R)-N-(2,4,6-Trimethoxyphenyl)-1-(3-methoxyphenyl)-2-{2-[(S)-p-tolyl-
sulfinyl]phenyl}ethylamine (5’’f): This compound was obtained as the
major diastereoisomer by using imine 3’’f and (S)-1 as the starting mate-
rials. Chromatography: n-hexane/AcOEt, 4:1; yield: 68%; yellow oil.
[a]2D0 =42.3 (c=0.8 in CHCl3). 1H NMR (300 MHz, CDCl3): d=7.72 (d,
J=6.6 Hz, 1H), 7.58 (d, J=8.1 Hz, 2H), 7.25–7.17 (m, 2H), 7.11–7.01 (m,
4H), 6.70 (m, 3H), 5.94 (s, 2H), 4.79 (t, J=7.4 Hz, 1H), 3.62 (s, 3H),
3.60 (s, 3H), 3.57 (s, 6H), 3.24–3.16 (m,1H), 3.09–3.04 (m, 1H), 2.34 ppm
(s, 3H). 13C NMR (75 MHz, CDCl3): d=159.3, 154.6, 151.8, 144.9, 143.6,
141.9, 141.1, 137.8, 130.6, 130.5, 129.7, 128.9, 127.3, 125.8, 125.6, 124.8,
119.0, 112.3, 112.1, 91.3, 61.3, 55.7, 55.2, 54.9, 39.9, 21.2 ppm.
A
sulfinyl]phenyl}propylamine (6’’d): This compound was obtained as the
minor diastereoisomer by using imine 3’’d and (S)-2 as the starting mate-
rials. Chromatography: n-hexane/AcOEt, 4:1; yield: 6%; yellow oil.
[a]2D0 =+115.1 (c=0.4 in CHCl3). 1H NMR (300 MHz, CDCl3): d=7.81
(d, J=7.8 Hz, 1H), 7.59–7.36 (m, 4H), 7.41–7.36 (m, 2H), 7.29 (d, J=
4.7 Hz, 3H), 7.14–7.10 (m, 2H), 5.91 (s, 2H), 4.71 (brs, 1H), 4.62 (d, J=
10.2 Hz, 1H), 3.78–3.70 (m, 1H), 3.66 (s, 3H), 3.62 (s, 6H), 2.38 (s, 3H),
0.87 ppm (d, J=7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): d=154.3,
151.5, 145.8, 145.2, 142.2, 142.4, 141.9, 141.2, 133.6, 131.6, 129.9, 128.8,
6192
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 6179 – 6195