J. A. Sirvent, F. Foubelo, M. Yus
FULL PAPER
(hexane/AcOEt, 3:1) yielded 4j (44 mg, 16%, diastereomeric mix-
ture, 3:1) as a yellow oil; Rf = 0.43 (hexane/AcOEt, 1:1). 1H NMR
(400 MHz, CDCl3, major isomer): δ = 7.62 (ddd, J = 7.9, 1.4 Hz,
1 H), 7.49 (dd, J = 8.0, 1.6 Hz, 1 H), 7.31–7.25 (m, 1 H), 7.11 (ddd,
J = 7.4, 6.5, 1.7 Hz, 1 H), 5.53–5.40 (m, 1 H), 5.18–5.09 (m, 1 H),
5.07–5.00 (m, 1 H), 4.58 (s, 1 H), 3.20 (dd, J = 13.9, 7.3 Hz, 1 H),
3.13 (dd, J = 13.9, 7.2 Hz, 1 H), 1.89 (s, 3 H), 1.23 (s, 9 H) ppm.
13C NMR (101 MHz, CDCl3, major isomer): δ = 142.5 (C), 136.0
(CH), 133.5 (CH), 129.05 (CH), 128.97 (CH), 127.5 (CH), 121.7
imine 3a (288 mg, 1.0 mmol), indium (143 mg, 1.25 mmol), and 3-
bromo-2-methylpropene (0.156 mL, 1.5 mmol). Purification by col-
umn chromatography (hexane/AcOEt, 3:1) yielded 4m (220 mg,
64%) as a white solid; m.p. 76–78 °C. Rf = 0.52 (hexane/AcOEt,
1:1). [α]2D0 = +165 (c = 1.02, CH2Cl2). 1H NMR (300 MHz, CDCl3):
δ = 7.55 (dd, J = 8.0, 1.2 Hz, 1 H), 7.48 (dd, J = 7.8, 1.6 Hz, 1 H),
7.30 (td, J = 7.5, 1.0 Hz, 1 H), 7.13 (td, J = 7.8, 1.7 Hz, 1 H), 5.00
(dd, J = 11.1, 3.8 Hz, 1 H), 4.96 (s, 1 H), 4.88 (s, 1 H), 3.72 (s, 1
H), 2.62 (dd, J = 13.7, 3.7 Hz, 1 H), 2.23 (dd, J = 13.8, 10.6 Hz, 1
H), 1.86 (s, 3 H), 1.22 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3):
(C), 119.6 (CH2), 61.1 (C), 56.4 (C), 45.4 (CH2), 26.3 (CH3), 23.0
1
(CH3) ppm. H NMR (400 MHz, CDCl3, minor isomer): δ = 7.60 δ = 142.3 (C), 141.4 (C), 133.2 (CH), 128.9 (CH), 128.7 (CH), 127.6
(dd, J = 8.3, 1.3 Hz, 1 H), 7.52 (dd, J = 8.0, 1.6 Hz, 1 H), 7.32–
7.25 (m, 1 H), 7.13–7.07 (m, 1 H), 5.53–5.40 (m, 1 H), 5.18–5.09
(m, 1 H), 5.08–5.00 (m, 1 H), 4.94 (s, 1 H), 3.02 (dd, J = 14.0,
(CH), 123.5 (C), 115.3 (CH2), 55.9 (C), 53.4 (CH), 46.1 (CH2), 22.7
(CH ), 21.5 (CH ) ppm. IR (ATR): ν = 3296, 1648, 1567, 1465,
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1060, 755 cm–1. LRMS (EI): m/z (%) = 233 (53), 231 (52), 225 (5),
7.2 Hz, 1 H), 2.93 (dd, J = 13.9, 7.3 Hz, 1 H), 1.83 (s, 3 H), 1.25 223 (6), 184 (15), 182 (14), 153 (89), 152 (100), 144 (14), 134 (14),
(s, 9 H) ppm. 13C NMR (101 MHz, CDCl3, minor isomer): δ =
142.7 (C), 135.7 (CH), 133.2 (CH), 129.4 (CH), 127.6 (CH), 122.0
(C), 118.9 (CH), 60.9 (C), 56.3 (C), 45.1 (CH2), 26.4 (CH3), 22.9
129 (13), 77 (12). HRMS (EI): calcd. for C11H1479BrNOS [M –
C4H8]+ 286.9979; found 286.9997.
(SS,1R)-1-(2-Bromophenyl)-N-(tert-butylsulfinyl)-2,2-dimethylbut-3-
en-1-amine (4n): The representative procedure was followed by
using imine 3a (242 mg, 0.84 mmol), indium (115 mg, 1.0 mmol),
and 3,3-dimethylallyl bromide (0.110 mL, 1.2 mmol). Purification
by column chromatography (hexane/AcOEt, 5:1) yielded 4n
(156 mg, 52%) as a yellow oil; Rf = 0.52 (hexane/AcOEt, 1:1). [α]
(CH ) ppm. IR (ATR): ν = 3217, 1638, 1462, 1427, 1061,
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1016 cm–1. LRMS (EI): m/z (%) = 274 (15), 272 (14), 247 (17), 245
(17), 208 (56), 184 (11), 182 (11), 167 (10), 166 (100), 144 (17), 130
(22), 129 (16), 115 (10), 103 (11), 102 (15), 91 (12). HRMS (EI):
calcd. for C10H1179BrNOS [M – C4H8]+ 271.9745; found 271.9752.
(SS,2R)-1-(2-Bromophenyl)-N-(tert-butylsulfinyl)-2-methylpent-4-
en-2-amine (4k): The representative procedure was followed by
using imine 3k (316 mg, 1.0 mmol), indium (143 mg, 1.25 mmol),
and allyl bromide (0.135 mL, 1.5 mmol). Purification by column
chromatography (hexane/AcOEt, 3:1) yielded 4k (237 mg, 66%) as
a colorless oil; Rf = 0.51 (hexane/AcOEt, 1:1). [α]2D0 = –20 (c = 1.04,
20
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= +108 (c = 1.05, CH2Cl2). H NMR (300 MHz, CDCl3): δ =
D
7.57 (dd, J = 8.0, 1.2 Hz, 1 H), 7.33 (dd, J = 7.9, 2.0 Hz, 1 H), 7.28
(td, J = 7.5, 1.2 Hz, 1 H), 7.13 (ddd, J = 8.0, 7.0, 2.0 Hz, 1 H),
5.98 (dd, J = 17.5, 10.7 Hz, 1 H), 5.24 (dd, J = 10.7, 1.1 Hz, 1 H),
5.17 (dd, J = 17.5, 1.1 Hz, 1 H), 4.90 (d, J = 2.3 Hz, 1 H), 3.74 (d,
J = 1.6 Hz, 1 H), 1.14 (s, 9 H), 1.11 (s, 3 H), 1.03 (s, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 145.5 (CH), 138.2 (C), 133.1
(CH), 131.1 (CH), 129.0 (CH), 126.7 (CH), 126.2 (C), 115.0 (CH2),
61.8 (CH), 55.8 (C), 43.1 (C), 25.8 (CH3), 22.7 (CH3), 20.5
1
CH2Cl2). H NMR (300 MHz, CDCl3): δ = 7.55 (d, J = 7.9 Hz, 1
H), 7.39 (dd, J = 7.7, 1.5 Hz, 1 H), 7.24 (t, J = 7.3 Hz, 1 H), 7.08
(td, J = 7.7, 1.6 Hz, 1 H), 6.06–5.89 (m, 1 H), 5.26 (s, 1 H), 5.24–
5.18 (m, 1 H), 3.60 (s, 1 H), 3.19 (d, J = 13.8 Hz, 1 H), 2.93 (d, J
= 13.8 Hz, 1 H), 2.57 (d, J = 7.4 Hz, 2 H), 1.29 (s, 3 H), 1.11 (s, 9
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 137.1 (C), 133.5 (CH),
133.1 (CH), 132.8 (CH), 128.3 (CH), 127.1 (CH), 126.5 (C), 120.0
(CH2), 59.0 (C), 56.1 (C), 47.5 (CH2), 45.8 (CH2), 25.0 (CH3), 22.7
(CH ) ppm. IR (ATR): ν = 3276, 1636, 1467, 1068, 1020 cm–1
.
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LRMS (EI): m/z (%) = 306 (11), 304 (11), 233 (66), 231 (65), 207
(17), 186 (64), 185 (14), 184 (83), 183 (11), 182 (17), 153 (10), 152
(100), 144 (10), 136 (20), 134 (12), 104 (12), 103 (10), 102 (15), 77
(17), 69 (10), 57 (28), 55 (12). HRMS (EI): calcd. for C7H679BrNOS
[M – C9H18]+ 232.9333; found 232.9328.
(CH ) ppm. IR (ATR): ν = 3222, 1436, 1048, 915, 747 cm–1. LRMS
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(EI): m/z (%) = 171 (5), 169 (5), 134 (5), 133 (7), 132 (100), 116 (6),
114 (6), 91 (6), 90 (11), 89 (8), 84 (6). HRMS (EI): calcd. for
C7H679Br [M – C9H18NOS]+ 168.9653; found 168.9658.
(SS,1R,1ЈR)-(2-Bromophenyl)-N-(tert-butylsulfinyl)(cyclohex-2-en-
1-yl)methanamine (4o): The representative procedure was followed
by using imine 3a (288 mg, 1 mmol), indium (143 mg, 1.25 mmol),
and 3-bromocyclohexene (0.155 mL, 1.5 mmol). Purification by
column chromatography (hexane/AcOEt, 4:1) yielded 4o (110 mg,
60%) as a white solid; m.p. 114–117 °C. Rf = 0.50 (hexane/AcOEt,
1:1). [α]2D0 = +150 (c = 0.93, CH2Cl2). 1H NMR (300 MHz, CDCl3):
δ = 7.55 (dd, J = 7.9, 1.2 Hz, 1 H), 7.40 (dd, J = 7.8, 1.8 Hz, 1 H),
7.31 (td, J = 7.5, 1.1 Hz, 1 H), 7.12 (td, J = 7.4, 1.8 Hz, 1 H), 6.02–
5.87 (m, 1 H), 5.55 (d, J = 10.0 Hz, 1 H), 4.75 (t, J = 4.4 Hz, 1 H),
3.64 (d, J = 4.3 Hz, 1 H), 2.73–2.60 (m, 1 H), 2.07–1.94 (m, 2 H),
1.93–1.75 (m, 2 H), 1.69–1.40 (m, 2 H), 1.20 (s, 9 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 141.4 (C), 133.2 (CH), 132.7 (CH),
129.2 (CH), 128.7 (CH), 127.2 (CH), 124.4 (CH), 123.5 (C), 61.4
(CH), 56.0 (C), 41.0 (CH), 27.0 (CH2), 25.2 (CH2), 22.8 (CH3),
(SS,3S)-1-(2-Bromophenyl)-N-(tert-butylsulfinyl)-3-methylhex-5-en-
3-amine (4l): The representative procedure was followed by using
imine 3l (369 mg, 1.11 mmol), indium (160 mg, 1.4 mmol), and allyl
bromide (0.151 mL, 1.68 mmol). Purification by column
chromatography (n-hexane/AcOEt, 1:1) yielded 4l (302 mg, 81%)
as a yellow oil; Rf = 0.47 (hexane/AcOEt, 1:1). [α]2D0 = +43 (c =
1.03, CH2Cl2). 1H NMR (300 MHz, CDCl3): δ = 7.51 (d, J =
7.8 Hz, 1 H), 7.26–7.21 (m, 2 H), 7.10–7.00 (m, 1 H), 5.97–5.78 (m,
1 H), 5.25–5.09 (m, 2 H), 3.38 (s, 1 H), 2.94–2.64 (m, 2 H), 2.53–
2.36 (m, 2 H), 1.84–1.72 (m, 2 H), 1.40 (s, 3 H), 1.24 (s, 9 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 141.5 (C), 133.3 (CH), 132.9
(CH), 130.6 (CH), 127.8 (CH), 127.8 (CH), 124.4 (C), 119.8 (CH2),
57.6 (C), 56.1 (C), 46.8 (CH2), 41.5 (CH2), 30.7 (CH2), 25.7 (CH3),
21.7 (CH ) ppm. IR (ATR): ν = 3248, 1469, 1049, 1036 cm–1
.
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22.9 (CH ) ppm. IR (ATR): ν = 3222, 1637, 1471, 1053, 1023,
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LRMS (EI): m/z (%) = 251 (12), 249 (12), 234 (45), 233 (77), 232
(23), 231 (74), 186 (21), 185 (11), 184 (43), 183 (9), 182 (23), 171
(18), 170 (32), 169 (16), 153 (11), 152 (100), 142 (10), 141 (10), 136
(16), 134 (14), 129 (11), 128 (12), 115 (11), 104 (11), 102 (13), 81
(20), 79 (11), 77 (22), 67 (13). HRMS (EI): calcd. for
C13H1679BrNOS [M – C4H8]+ 313.0136; found 313.0101.
748 cm–1. LRMS (EI): m/z (%) = 317 (2) [M – 56 (81Br)]+, 315 (2),
302 (2), 300 (2), 275 (23), 273 (22), 236 (45), 226 (4), 224 (5), 211
(4), 209 (4), 194 (7), 171 (49), 169 (50), 146 (61), 133 (17), 132 (100),
131 (11), 116 (16), 104 (16), 103 (12), 91 (27), 90 (24), 89 (15), 84
(42), 77 (22), 55 (11). HRMS (EI): calcd. for C13H1879BrNOS [M –
C4H8]+ 315.0292; found 315.0320.
(SS,1R)-1-(2-Bromophenyl)-N-(tert-butylsulfinyl)-3-methylbut-3-en- General Procedure for the Intramolecular Heck Reaction of Homoal-
1-amine (4m): The representative procedure was followed by using lylamine Derivatives 4. Synthesis of Methylene Carbocycles 5: A
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Eur. J. Org. Chem. 2013, 2461–2471