Benzazepines by Gold-Catalysed Reactions of N-Allenylamides
(300 MHz, CDCl3): δ = 1.29 (t, J = 6.8 Hz, 3 H, CH3CH2O), 2.28 127.4, 127.9, 129.1, 129.4, 129.7, 130.0, 131.0, 133.5, 134.1, 134.2,
(br. s, 1 H, 3-H), 2.37 (s, 3 H, CH3Ar), 3.35 (s, 3 H, CH3O), 3.40
136.3, 136.7, 137.2, 143.8, 143.9 ppm. IR (film): ν = 1600 cm–1.
˜
1
2
1
2
(dd, J = 8.8, J = 2.7 Hz, 1 H, CH2OCH3), 3.53 (dd, J = 8.8, J
= 5.2 Hz, 1 H, CH2OCH3), 3.74–3.84 (m, 1 H, CH3CH2O), 4.06–
4.16 (m, 1 H, CH3CH2O), 5.56–5.65 (m, 2 H, 4-H and 5-H), 5.78
(d, J = 10.4 Hz, 1 H, 2-H), 6.91–6.95 (m, 1 H, ArH), 7.09 (d, J =
8.2 Hz, 2 H, ArH), 7.22 (d, J = 8.2 Hz, 2 H, ArH), 7.27–7.34 (m,
2 H, ArH), 7.52–7.56 (m, 1 H, ArH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 14.9, 21.5, 43.5, 59.1, 63.1, 71.8, 97.2, 127.8, 128.0,
128.2, 128.5, 128.6, 129.8, 131.0, 133.4, 133.8, 136.0, 138.3,
2-Phenyl-1-tosyl-1H-indole (6d): Table 1, Entry 13: reaction tem-
perature, time: –78 °C, 4 h. Yield: 76 mg (22%). Brown solid (m.p.
143–145 °C). 1H NMR (300 MHz, CDCl3): δ = 2.30 (s, 3 H,
CH3Ar), 6.56 (s, 1 H, ArH), 7.05 (d, J = 8.3 Hz, 2 H, ArH), 7.25–
7.30 (m, 4 H, ArH), 7.37 (td, 1J = 7.3, 2J = 1.5 Hz, 1 H, ArH),
7.41–7.47 (m, 3 H, ArH), 7.51–7.55 (m, 2 H, ArH), 8.33 (d, J =
8.3 Hz, 1 H, ArH) ppm. 13C NMR (75 MHz, CDCl3): δ = 21.5,
113.6, 116.6, 120.6, 124.3, 124.7, 126.7, 127.5, 128.6, 129.2, 130.3,
142.9 ppm. IR (film): ν = 1590 cm–1. C H NO S (387.49): calcd.
˜
21 25
4
130.5, 132.4, 134.5, 138.2, 142.1, 144.5 ppm. IR (KBr): ν =
˜
C 65.09, H 6.50, N 3.61; found C 65.31, H 6.26, N 3.86.
1590 cm–1. C21H17NO2S (347.43): calcd. C 72.60, H 4.93, N 4.03;
found C 72.83, H 4.68, N 4.24.
(1S)-1-({[2-Methoxy-3-(methoxymethyl)-2,3-dihydro-1H-1-
benzazepinyl]sulfonyl}methyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-
one (4ia): Table 2, Entry 5: reaction temperature, time: –78 °C, 4 h.
Solvent: DCM (with ethanol traces)/MeOH. Yield: 205 mg (46%).
(1S)-1-[(1H-Indol-1-ylsulfonyl)methyl]-7,7-dimethylbicyclo[2.2.1]-
heptan-2-one (6i): Table 2, Entry 5: reaction temperature, time:
–78 °C, 4 h. Solvent: DCM (with ethanol traces)/MeOH. Yield:
36 mg (11%). Yellow oil. 1H NMR (300 MHz, CDCl3): δ = 0.86 (s,
3 H, CH3camphor), 1.18 (s, 3 H, CH3camphor), 1.45–1.54 (m, 1
H, CH2camphor), 1.76–1.85 (m, 1 H, CH2camphor), 1.97 (d, J =
18.9 Hz, 1 H, CH2camphor), 2.06–2.16 (m, 2 H, CH2camphor),
1
Yellow oil. H NMR (300 MHz, CDCl3) (mixture of isomers, 7:3):
δ = 0.72 (s, 0.9 H, CH3camphor), 0.87 (s, 2.1 H, CH3camphor),
0.96 (s, 0.9 H, CH3camphor), 1.16 (s, 2.1 H, CH3camphor), 1.23
(t, J = 7.1 Hz 3 H, CH3CH2O), 1.31–1.45 (m, 1 H, CH2camphor),
1.81–2.05 (m, 2 H, CH2camphor), 2.28–2.50 (m, 5 H, 3-H and
CH2camphor), 2.66 (d, J = 14.8 Hz, 0.3 H, SCH2camphor), 2.77
(d, J = 14.8 Hz, 0.7 H, SCH2camphor), 3.24 (d, J = 14.8 Hz, 0.7
H, SCH2camphor), 3.35 (d, J = 14.8 Hz, 0.3 H, SCH2camphor),
3.38 (s, 3 H, CH3O), 3.45–3.52 (m, 1 H, CH2OCH3), 3.56–3.60 (m,
1 H, CH2OCH3), 3.63–3.74 (m, 1 H, CH3CH2O), 3.95–4.05 (m, 1
H, CH3CH2O), 5.63–5.66 (m, 1 H, 5-H), 6.11–6.20 (m, 1 H, 4-H),
1
2
2.39 (dt, J = 18.3, J = 3.0 Hz, 1 H, CH2camphor), 2.51–2.61 (m,
1 H, CHcamphor), 3.08 (d, J = 14.6 Hz, 1 H, SCH2camphor), 3.63
(d, J = 14.6 Hz, 1 H, SCH2camphor), 6.72 (d, J = 3.0 Hz, 1 H,
ArH), 7.32 (td, 1J = 7.3, 2J = 1.2 Hz, 1 H, ArH), 7.40 (td, 1J =
2
7.9, J = 1.2 Hz, 1 H, ArH), 7.48 (d, J = 3.7 Hz, 1 H, ArH), 7.65
(d, J = 7.3 Hz, 1 H, ArH), 8.01 (dd, 1J = 7.9, 2J = 1.2 Hz, 1 H,
ArH) ppm. 13C NMR (75 MHz, CDCl3): δ = 19.7, 19.9, 25.2, 26.9,
42.4, 42.8, 48.0, 50.5, 58.5, 108.4, 113.1, 121.5, 123.3, 124.8, 126.2,
1
2
6.67 (m, 1 H, 2-H), 6.72 (dd, J = 10.4, J = 2.2 Hz, 1 H, ArH),
7.21–7.41 (m, 2 H, Ar), 7.47–7.49 (m, 1 H, Ar) ppm. 13C NMR
(75 MHz, CDCl3) (mixture of isomers, 7:3): δ = 14.9, 19.6, 19.7,
20.0, 20.3, 25.0, 25.2, 26.7, 26.8, 42.4, 42.5, 42.7, 42.9, 44.3, 47.4,
47.6, 49.1, 49.2, 58.5, 58.6, 59.1, 59.2, 63.2, 71.9, 72.0, 96.9, 97.0,
128.0, 128.1, 128.6, 128.7, 128.8, 128.8, 130.6, 131.1, 132.6, 133.1,
133.2, 133.3, 134.3, 134.5, 137.4, 137.5, 191.9, 192.1 ppm. IR (film):
130.6, 134.8, 193.0 ppm. IR (film): ν = 1740 cm–1. C H NO S
˜
18 21
3
(331.43): calcd. C 65.23, H 6.39, N 4.23; found C 65.39, H 6.16, N
3.94.
N-[(1E)-3-Ethoxyprop-1-enyl]-4-methyl-N-phenylbenzenesulfon-
amide (10): Reaction temperature, time: –78 °C, 1 h. Yield: 198 mg
1
ν = 1740, 1600 cm–1.
(60%). Yellow oil. H NMR (300 MHz, CDCl3): δ = 1.16 (t, J =
˜
6.8 Hz, 3 H, CH3CH2), 2.43 (s, 3 H, CH3Ar), 3.41 (q, J = 6.8 Hz,
1
2
2 H, CH3CH2), 3.89 (dd, J = 1.0, J = 6.8 Hz, 2 H, CH2), 4.43–
4.53 (m, 1 H, CH=), 6.97–7.00 (m, 2 H, NCH= and ArH), 7.22–
7.28 (m, 3 H, ArH), 7.34–7.36 (m, 2 H, ArH), 7.55 (d, J = 8.3 Hz, 2
H, ArH), 7.57 (d, J = 7.8 Hz, 1 H, ArH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 15.1, 21.6, 65.3, 69.3, 107.0, 127.5, 129.1, 129.5, 129.6,
2-Ethoxy-3-(ethoxymethyl)-1-tosyl-2,3-dihydro-1H-1-benzazepine
(4ac): Table 2, Entry 6: reaction temperature, time: –78 °C, 1 h.
1
Yield: 325 mg (81%). Yellow oil. H NMR (300 MHz, CDCl3): δ
= 1.22 (t, J = 6.8 Hz, 3 H, CH3CH2O), 1.28 (t, J = 6.8 Hz, 3 H,
CH3CH2O), 2.28 (br. s, 1 H, 3-H), 2.36 (s, 3 H, CH3Ar), 3.41–3.59
(m, 4 H, 2 CH3CH2O), 3.74–3.84 (m, 1 H, CH2CH), 4.05–4.15 (m,
1 H, CH2CH), 5.56–5.64 (m, 2 H, 4-H and 5-H), 5.80 (d, J =
10.3 Hz, 1 H, 2-H), 6.91–6.94 (m, 1 H, ArH), 7.09 (d, J = 8.3 Hz,
2 H, ArH), 7.23 (d, J = 8.3 Hz, 2 H, ArH), 7.27–7.31 (m, 2 H,
ArH), 7.51–7.54 (m, 1 H, ArH) ppm. 13C NMR (75 MHz, CDCl3):
δ = 14.9, 15.0, 21.4, 43.5, 63.0, 66.5, 69.4, 97.3, 127.6, 127.9, 128.1,
128.5, 128.6, 129.5, 131.3, 133.4, 133.9, 136.2, 138.2, 142.9 ppm.
130.3, 132.3, 135.7, 136.1, 144.0 ppm. IR (film): ν = 1600 cm–1.
˜
C18H21NO3S (331.43): calcd. C 65.23, H 6.39, N 4.23; found C
64.89, H 6.07, N 4.45.
N-(3-Methoxyprop-1-enyl)-4-methyl-N-(2-vinylphenyl)benzenesul-
fonamide (11): Reaction temperature, time: –78 °C, 2 h. Yield:
1
223 mg (65%). Yellow oil. H NMR (300 MHz, CDCl3): δ = 2.43
(s, 3 H, CH3), 3.23 (s, 3 H, CH3O), 3.82–3.85 (m, 2 H, CH2), 4.26–
4.35 (m, 1 H, CH2CH=), 5.21 (d, J = 11.2 Hz, 1 H, CH2=CH),
5.71 (d, J = 17.5 Hz, 1 H, CH2=CH), 6.66–6.75 (m, 2 H, CH2=CH
and NCH=), 7.16–7.22 (m, 2 H, ArH), 7.28 (d, J = 8.3 Hz, 2 H,
ArH), 7.36 (t, J = 7.3 Hz, 1 H, ArH), 7.60 (d, J = 7.8 Hz, 2 H,
ArH), 7.69 (d, J = 7.8 Hz, 1 H, ArH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 21.5, 57.3, 70.9, 106.7, 116.2, 126.2, 127.5, 128.5,
129.5, 129.6, 130.0, 131.5, 132.1, 133.4, 135.9, 137.9, 144.1 ppm.
IR (film): ν = 1600 cm–1. C H NO S (401.52): calcd. C 65.81, H
˜
22 27
4
6.78, N 3.49; found C 66.02, H 6.55, N 3.60.
2-(Ethylsulfanyl)-3-[(ethylsulfanyl)methyl]-1-tosyl-2,3-dihydro-1H-1-
benzazepine (4ad): Table 2, Entry 7: reaction temperature, time:
1
–78 °C, 3 h. Yield: 333 mg (77%). Yellow oil. H NMR (300 MHz,
CDCl3) (mixture of isomers, 1:1): δ = 1.23–1.30 (m, 6 H,
CH3CH2S), 1.55–1.67 (m, 1.5 H, CH2CH), 1.75–1.89 (m, 0.5 H,
CH2CH), 2.29–2.76 (m, 4.5 H, CH3CH2S, CH), 2.41 (s, 3 H,
CH3Ar), 2.91–2.96 (m, 0.5 H, CH3CH2S), 5.48 (d, J = 8.8 Hz, 1
IR (film): ν = 3050, 2920, 2820, 1650, 1600 cm–1. C H NO S
˜
19 21
3
(343.44): calcd. C 66.45, H 6.16, N 4.08; found C 66.63, H 5.97, N
4.29.
1
2
H, 5-H), 5.73 (dd, J = 8.8, J = 5.4 Hz, 1 H, 4-H), 6.88 (d, J =
7.8 Hz, 1 H, 2-H), 7.22–7.36 (m, 4 H, ArH), 7.45–7.51 (m, 1 H, Supporting Information (see footnote on the first page of this arti-
ArH), 7.62–7.72 (m, 3 H, ArH) ppm. 13C NMR (75 MHz, [D6]- cle): Additional experimental procedures and characterization data
DMSO) (mixture of isomers, 1:1): δ = 14.6, 14.6, 14.7, 14.8, 21.1,
for 8, 1b, 1g, 1h, 1i, 1c, 1d and 9 and NMR spectra for all new
21.2, 24.5, 24.8, 25.0, 26.3, 27.9, 28.0, 34.4, 34.9, 65.3, 65.4, 125.9, compounds.
Eur. J. Org. Chem. 2009, 5057–5062
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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