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C. Theeraladanon et al. / Tetrahedron 60 (2004) 3017–3035
purified by column chromatography on silica gel (n-hexane/
AcOEt¼5:1) to give 266 mg (97%) of 47 as a colorless oil.
1H NMR (CDCl3) d 7.66 (2H, d, J¼8.3 Hz), 7.27–7.31 (4H,
m), 7.16 (1H, dd, J¼2.7, 8.0 Hz), 6.80 (1H, d, J¼7.6 Hz),
5.54–5.64 (1H, m), 5.22 (1H, s), 5.05 (1H, s), 4.91–4.96
(2H, m), 3.53 (2H, br), 2.44 (3H, s), 2.18 (3H, s), 2.08 (2H,
br); 13C NMR (CDCl3) d 144.9, 143.6, 143.4, 136.7, 136.4,
134.5, 130.2, 129.4, 128.3, 128.2, 128.1, 127.4, 116.9,
116.7, 50.8, 32.3, 24.4, 21.5; IR (neat) 3461, 3070, 2958,
2902, 2865, 1646, 1596, 1491, 1450, 1341, 1158,
1091 cm21; LRMS (EI) m/z 341 [20, Mþ], 186 [100].
Anal. Calcd for C20H23NO2S: C, 70.35; H, 6.79; N, 4.10;
found: C, 70.26; H, 6.94; N, 3.96.
purified by column chromatography on silica gel (n-hexane/
AcOEt¼5:1) to give 347 mg (98%) of 50 as a colorless oil.
1H NMR (CDCl3) d 7.66 (2H, d, J¼8.3 Hz), 7.25–7.31 (4H,
m), 7.16 (1H, dd, J¼2.7, 6.3 Hz), 6.78 (1H, d, J¼8.3 Hz),
5.60–5.70 (1H, m), 5.21 (1H, s), 5.05 (1H, s), 4.91 (2H, d,
J¼12.4 Hz), 3.47 (2H, br), 2.44 (3H, s), 2.18 (3H, s), 1.94
(2H, d, J¼7.0 Hz), 1.48 (2H, br); 13C NMR (CDCl3) d
145.0, 143.6, 143.3, 137.3, 136.72, 136.69, 130.2, 129.4,
128.2, 128.12, 128.07, 127.4, 116.7, 115.2, 51.2, 30.9, 26.9,
24.4, 21.5; IR (neat) 3461, 3076, 2977, 2924, 1638, 1598,
1488, 1347, 1162, 1092 cm21; LRMS (EI) m/z 355 [10,
Mþ], 200 [100]. Anal. Calcd for C21H25NO2S C, 70.95; H,
7.09; N, 3.94; found C, 71.03; H, 7.31; N, 3.81.
2.1.42. [N,N0-Bis(o-isopropenylphenyl)-N,N0-bis-p-toluene-
sulfonyl]hex-3-ene-1,6-diamine (48). To a solution of
olefin 47 (102 mg, 0.30 mmol) in 30 mL of CH2Cl2 under
an Ar atmosphere, was added catalyst A (12.3 mg,
0.006 mmol). The mixture was degassed and stirred at
50 8C for 1 h. After removal of the solvent, the residue was
purified by column chromatography on silica gel (n-hexane/
CH2Cl2¼1:1) to give 36 mg (70%, E/Z mixture) of 48 as a
2.1.45. [N,N0-Bis(o-isopropenylphenyl)-N,N0-bis-p-toluene-
sulfonyl]oct-4-ene-1,8-diamine (51). To a solution of
olefin 50 (60 mg, 0.17 mmol) in 17 mL of CH2Cl2 under
an Ar atmosphere, was added catalyst A (7.0 mg,
0.0085 mmol). The mixture was degassed and stirred at
50 8C for 4 h. After removal of the solvent, the residue was
purified by column chromatography on silica gel (n-hexane/
CH2Cl2¼1:1) to give 26 mg (70%, E/Z mixture) of 51 as a
1
1
colorless oil. H NMR (CDCl3) d 7.62 (4H, dd, J¼8.3,
colorless oil. H NMR (CDCl3) d 7.64 (4H, dd, J¼1.7,
11.5 Hz), 7.26–7.30 (8H, m), 7.09–7.16 (2H, m), 6.72 (2H,
dd, J¼4.9, 7.6 Hz), 5.14–5.19 (4H, m), 5.01 (2H, s), 3.40
(4H, br), 2.44 (6H, s), 2.15 (6H, s), 1.97 (4H, br); 13C NMR
(CDCl3) d 144.8, 143.6, 143.4, 136.6, 130.2, 129.5, 128.5,
128.2, 128.1, 128.0, 127.6, 127.4, 127.3, 116.7, 53.4, 51.1,
50.8, 31.2, 26.2, 24.3, 21.5, 14.1; IR (neat) 3451, 3060,
8.2 Hz), 7.24–7.30 (8H, m), 7.11–7.15 (2H, m), 6.77 (2H,
dd, J¼8.1, 8.1 Hz), 5.16–5.19 (4H, m), 5.01 (2H, s), 4.43
(4H, br), 2.43 (6H, s), 2.16 (6H, s), 1.82 (4H, s), 1.39 (4H,
br); 13C NMR (CDCl3) d 144.9, 143.62, 143.61, 143.4,
143.3, 136.6, 136.66, 136.63, 130.2, 129.6, 129.4, 129.2,
128.2, 128.17, 128.09, 128.05, 127.4, 116.6, 51.24, 51.18,
29.7, 27.7, 27.5, 24.5, 24.4, 21.5; IR (neat) 3442, 2921,
2856, 1637, 1441, 1345, 1159 cm21; LRMS (EI) 682 [15,
Mþ] 158 [100]. Anal. Calcd for C40H46N2O4S21/2H2O C,
69.43; H, 6.85; N, 4.05; found C, 69.17; H, 6.94; N, 3.77.
3023, 2921, 2846, 1637, 1598, 1489, 1346, 1160 cm21
;
LRMS (FAB) m/z 655 [10, MþþH], 144 [100]. Anal. Calcd
for C38H42N2O4S2: C, 69.69; H, 6.46; N, 4.28; found: C,
69.35; H, 6.54; N, 4.15.
2.1.43. 5-Methyl-1-p-toluenesulfonyl-2,3-dihydro-1H-
benzo[b]azepine (49). To a solution of olefin 47 (102 mg,
0.30 mmol) in 30 mL of CH2Cl2 under an Ar atmosphere,
was added catalyst B (12.7 mg, 0.006 mmol). The mixture
was degassed and stirred at 50 8C for 1 h. After removal of
the solvent, the residue was purified by column chroma-
tography on silica gel (n-hexane/AcOEt¼1:1), followed by
recrystallization from n-hexane/AcOEt to give 90 mg (96%)
of 49 as white prisms. Mp 92 8C; 1H NMR (CDCl3) d 7.52
(1H, dd, J¼1.7, 7.5 Hz), 7.42 (2H, d, J¼8.3 Hz), 7.23–7.34
(2H, m), 7.15–7.17 (3H, m), 5.61 (1H, dd, J¼1.2, 6.6 Hz),
4.13 (2H, br), 2.37 (3H, s), 2.05–2.10 (2H, m), 1.54 (3H, s);
13C NMR (CDCl3) d 142.6, 140.8, 137.8, 136.5, 136.2,
131.9, 129.0, 128.1, 127.5, 127.4, 127.1, 125.6, 57.2, 26.3,
22.0, 21.4; IR (KBr) 3451, 2921, 2884, 2846, 1655, 1339,
1160 cm21; LRMS (EI) m/z 313 [100, Mþ]. Anal. Calcd for
C18H19NO2S C, 68.98; H, 6.11; N, 4.47; found C, 68.76; H,
6.07; N, 4.33.
2.1.46. 6-Methyl-1-p-toluenesulfonyl-1,2,3,4-tetrahydro-
1H-benzo[b]azocine (52). To a solution of olefin 50
(275 mg, 0.77 mmol) in 77 mL of CH2Cl2 under an Ar
atmosphere, was added catalyst B (32.9 mg, 0.015 mmol).
The mixture was degassed and stirred at 50 8C for 4 h. After
removal of the solvent, the residue was purified by column
chromatography on silica gel (n-hexane/AcOEt¼10:1)
followed by recrystallization from n-hexane/AcOEt to
1
give 234 mg (86%) of 52 as white prisms. Mp 111 8C; H
NMR (CDCl3) d 7.62 (2H, d, J¼7.9 Hz), 7.25–7.34 (4H,
m), 7.15 (1H, dd, J¼2.4, 8.3 Hz), 6.76 (1H, d, J¼7.6 Hz),
5.73 (1H, dd, J¼1.2, 7.9 Hz), 4.21 (1H, br), 2.84 (1H, br),
2.43 (3H, s), 2.18 (1H, br), 2.06 (3H, s), 1.60 (3H, br); 13C
NMR (CDCl3) d 143.7, 142.8, 138.6, 138.1, 133.7, 129.3,
129.0, 128.6, 128.3, 127.8, 127.3, 126.9, 51.5, 26.7, 26.4,
24.3, 21.5; IR (KBr) 3451, 2934, 2856, 1488, 1342,
1159 cm21; LRMS (EI) m/z 327 [3, Mþ], 91 [100]. Anal.
Calcd for C19H21NO2S: C, 69.69; H, 6.46; N, 4.28; found C,
69.72; H, 6.47; N, 4.23.
2.1.44. N-n-Pentenyl-N-p-toluenesulfonyl-2-isopropenyl-
aniline (50). To a solution of N-p-toluenesulfonyl-2-iso-
propenylaniline (287 mg, 1.00 mmol) and K2CO3 (207 mg,
1.50 mmol) in 10 mL of DMF under an Ar atmosphere,
was added 5-bromo-1-pentene (0.18 mL, 1.50 mmol). The
mixture was stirred at 80 8C for 1 h and the reaction was
quenched by the addition of saturated aqueous NaHCO3.
The mixture was extracted with Et2O and the combined
organic layers were washed with brine and dried over
Na2SO4. After removal of the solvent, the residue was
2.1.47. N-Allyl-N-p-toluenesulfonyl-2-(1-methoxyvinyl)-
aniline (53a). To a solution of 2-aminoacetophenone
(400 mg, 3.00 mmol) in 20 mL of CH2Cl2 under an Ar
atmosphere, were added pyridine (0.72 mL, 9.00 mmol) and
TsCl (686 mg, 3.60 mmol). The mixture was stirred at room
temperature for 1 h and the reaction was quenched by the
addition of water. The mixture was extracted with AcOEt
and the combined organic layers were washed with brine
and dried over Na2SO4. After removal of the solvent, the