Base-Catalyzed Anti-Markovnikov Hydroamination of Vinylarenes
FULL PAPER
8.6 Hz, 2 H, aryl-H), 6.86 (d, 3JH,H = 8.6 Hz, 2 H, aryl-H), 3.82 (s,
(NHCH2CH2CH3) ppm. MS (FAB, 3-NBA): m/z (%) = 164 (100)
[M]+. C11H17N (163.26): calcd. C 80.93, H 10.50, N 8.58; found C
80.77, H 10.28, N 8.39. The spectroscopic data are in agreement
2
3 H, OCH3), 3.75 (d, JH,H = 13.1 Hz, 1 H, NHCH2Ar), 3.70 (d,
2JH,H = 13.1 Hz, 1 H, NHCH2Ar), 3.00 (m, 1 H, PhCH(CH3)-
3
CH2NH), 2.81 (d, JH,H = 4.5 Hz, 2 H, PhCH(CH3)CH2NH), 1.45 with previously published data.[11]
(br. s, 1 H, NH), 1.29 (d, 3JH,H = 6.9 Hz, 3 H, CH3) ppm. 13C{1H}
(Benzhydryl)(phenethyl)amine (3o): Purification by column
NMR (100.6 MHz, CDCl3, 25 °C): δ = 158.5, 145.4, 132.4, 129.1,
128.5, 127.2, 126.3, 113.7 (aryl), 56.2 (NHCH2Ar), 55.2 (OCH3),
53.2 (PhCH(CH3)CH2NH), 40.0 (PhCH(CH3)CH2NH), 20.1
(CH3) ppm. MS (FAB, 3-NBA): m/z (%) = 256 (18) [M]+, 121 (100)
[CH3OC6H4CH2]+. C17H21NO (255.36): calcd. C 79.96, H 8.29, N
5.49; found C 80.00, H 8.01, N 5.42.
chromatography on silica gel (CH2Cl2 + a few drops of Et3N, Rf =
1
0.45). H NMR (400 MHz, CDCl3, 25 °C): δ = 7.36–7.34 (m, 4 H,
aryl-H), 7.28–7.24 (m, 6 H, aryl-H), 7.20–7.16 (m, 5 H, aryl-H),
4.82 (s, 1 H, NHCHPh2), 2.84–2.80 (s, 4 H, PhCH2CH2NH), 1.57
(br. s, 1 H, NH) ppm. 13C{1H} NMR (100.6 MHz, CDCl3): δ =
144.1, 140.1, 128.7, 128.43, 128.37, 127.2, 126.9, 126.0 (aryl), 67.3
(NHCHPh2), 49.3 (PhCH2CH2NH), 36.5 (PhCH2CH2NH) ppm.
MS (FAB, 3-NBA): m/z (%) = 288 (22) [M]+, 210 (10) [M – Ph]+,
167 (100) [M – NHCH2CH2Ph]+. C21H21N (287.40): calcd. C 87.76,
H 7.36, N 4.87; found C 87.76, H 7.41, N 4.78.
Benzyl(1-methyl-2-phenylethyl)amine (3k): Purification by column
chromatography on silica gel (CH2Cl2 + a few drops of Et3N, Rf =
0.02). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.30–7.15 (m, 10
H, aryl-H), 3.85 (d, 2JH,H = 13.3 Hz, 1 H, NCH2Ph), 3.74 (d, 2JH,H
= 13.3 Hz, 1 H, NCH2Ph), 3.01–2.90 (m, 1 H, PhCH2CH(CH3)-
Benzylbis(phenethyl)amine (4a): Purification by column chromatog-
raphy on silica gel (CH2Cl2 + a few drops of Et3N, Rf = 0.09).
NH), 2.78 (m,
1
H, PhCH2CH(CH3)NH), 2.65 (m,
1
H,
=
3
PhCH2CH(CH3)NH), 1.63 (br. s, 1 H, NH), 1.10 (d, JH,H
1
Isolated yield: 21% (based on the amine for Table 1, Entry 4). H
6.2 Hz, 3 H, CH3) ppm. 13C{1H} NMR (100.6 MHz, CDCl3,
NMR (400 MHz, CDCl3, 25 °C): δ = 7.29–7.12 (m, 10 H, aryl-H),
3.73 (s, 2 H, NCH2Ph), 2.79 (s, 8 H, PhCH2CH2N) ppm. 13C{1H}
NMR (100.6 MHz, CDCl3, 25 °C): δ = 140.6, 139.6, 128.8, 128.7,
128.3, 128.1, 126.8, 125.8 (aryl), 58.5 (NCH2Ph), 55.7
(PhCH2CH2N), 33.6 (PhCH2CH2N) ppm. MS (FAB, 3-NBA): m/z
(%) = 316 (76) [M]+, 224 (100) [M – CH2Ph]+. HRMS (EI): calcd.
for C23H25N 315.1982; found 315.1950. The spectroscopic data are
in agreement with previously published data.[5l]
25 °C): δ = 140.4, 139.4, 129.3, 128.3, 127.9, 126.8, 126.1 (aryl),
53.7
(NHCH2Ph),
51.2
(PhCH2CH(CH3)NH),
43.5
(PhCH2CH(CH3)NH), 20.2 (CH3) ppm. MS (FAB, 3-NBA): m/z
(%) = 226 (100) [M]+, 134 (52) [M – CH2Ph]+. The spectroscopic
data are in agreement with previously published data.[5h,13c]
(4-Methoxybenzyl)(1-methyl-2-phenylethyl)amine (3l): Purification
by column chromatography on silica gel (CH2Cl2 + a few drops of
Et3N, Rf = 0.42). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.30 (m,
2 H, aryl-H), 7.23 (m, 1 H, aryl-H), 7.17 (m, 4 H, aryl-H), 6.84 (d,
3JH,H = 8.4 Hz, 2 H, aryl-H), 3.82 (d, 1 H, NCH2Ar, obscured by
(4-Methoxybenzyl)bis(phenethyl)amine (4b): Purification by column
chromatography on silica gel (CH2Cl2 + a few drops of Et3N, Rf =
0.07). Isolated yield: 20% (based on the amine for Table 2, En-
2
3
try 2). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.28 (t, JH,H
=
another signal), 3.80 (s, 3 H, OCH3), 3.69 (d, JH,H = 12.9 Hz, 2
H, NHCH2Ar), 3.00–2.92 (m, 1 H, PhCH2CH(CH3)NH), 2.79 (m,
1 H, PhCH2CH(CH3)NH), 2.66 (m, 1 H, PhCH2CH(CH3)NH),
7.4 Hz, 4 H, aryl-H), 7.22–7.18 (m, 4 H, aryl-H), 7.16–7.14 (m, 4
3
H, aryl-H), 6.84 (d, JH,H = 8.6 Hz, 2 H, aryl-H), 3.82 (s, 3 H,
3
1.51 (br. s, 1 H, NH), 1.11 (d, JH,H = 6.2 Hz, 3 H, CH3) ppm.
OMe), 3.69 (s, 2 H, NCH2Ar), 2.80 (s, 8 H, PhCH2CH2N) ppm.
13C{1H} NMR (100.6 MHz, CDCl3, 25 °C): δ = 158.5, 140.6,
131.5, 129.8, 128.8, 128.2, 125.8, 113.5 (aryl), 57.7 (NCH2Ar), 55.4
(OMe), 55.2 (PhCH2CH2N), 33.5 (PhCH2CH2N-) ppm. MS (FAB,
3-NBA): m/z (%) = 346 (8) [M]+, 344 (24) [M – H2]+, 254 (24) [M –
CH2Ph]+, 121 (100) [CH3C6H4CH2]+. C24H27NO (345.49): calcd.
C 83.44, H 7.88, N 4.05; found C 83.21, H 7.96, N 3.91. The spec-
troscopic data are in agreement with previously published data.[5l]
13C{1H} NMR (100.6 MHz, CDCl3, 25 °C): δ = 158.5, 139.4,
132.6, 129.1, 129.0, 128.3, 126.1, 113.7 (aryl), 55.2 (OCH3), 53.6
(PhCH2CH(CH3)NH), 50.6 (NHCH2Ar), 43.5 (PhCH2CH(CH3)-
NH), 20.1 (CH3) ppm. MS (FAB, 3-NBA): m/z (%) = 256 (38)
[M]+, 121 (100) [CH3OC6H4CH2]+. C17H21NO (255.36): calcd. C
79.96, H 8.29, N 5.48; found C 79.87, H 8.38, N 5.42. The spectro-
scopic data are in agreement with previously published data.[13d]
(Phenethyl)phenylamine (3m): Purification by column chromatog-
raphy on silica gel (CH2Cl2/MeOH, 95:5 + a few drops of Et3N, Rf
Benzylbis[2-(p-tolyl)ethyl]amine (4c): Purification by column
chromatography on silica gel (CH2Cl2 + a few drops of Et3N, Rf =
1
1
= 0.65). H NMR (400 MHz, CDCl3, 25 °C): δ = 7.38–7.34 (m, 2
0.05). H NMR (400 MHz, CDCl3, 25 °C): δ = 7.30–7.20 (m, 5 H,
3
3
3
H, aryl-H), 7.29–7.20 (m, 5 H, aryl-H), 6.75 (t, JH,H = 7.3 Hz, 1
aryl-H), 7.07 (d, JH,H = 7.9 Hz, 4 H, aryl-H), 7.02 (d, JH,H
8.0 Hz, 4 H, aryl-H), 3.73 (s, 2 H, NCH2Ph), 2.76 (s, 8 H,
CH2CH2N), 2.32 (s,
H, CH3C6H4) ppm. 13C{1H} NMR
=
3
H, aryl-H), 6.65 (d, JH,H = 7.8 Hz, 2 H, aryl-H), 3.69 (br. s, 1 H,
3
3
NH), 3.43 (t, JH,H = 6.8 Hz, 2 H, PhCH2CH2N), 2.95 (t, JH,H
=
3
7.1 Hz, 2 H, PhCH2CH2N) ppm. 13C{1H} NMR (100.6 MHz,
CDCl3, 25 °C): δ = 147.9, 139.3, 129.2, 128.7, 128.5, 126.4, 117.4,
112.9 (aryl), 45.0 (PhCH2CH2N), 35.5 (PhCH2CH2N) ppm. MS
(FAB, 3-NBA): m/z (%) = 198 (98) [M]+, 197 (100) [M – H]+. The
spectroscopic data are in agreement with previously published
data.[12b,13b]
(100.6 MHz, CDCl3, 25 °C): δ = 139.7, 137.5, 135.3, 129.0, 128.7,
128.6, 128.1, 126.7 (aryl), 58.5 (NHCH2Ph), 55.8 (CH2CH2N), 33.2
(CH2CH2N), 21.0 (CH3C6H4) ppm. MS (FAB, 3-NBA): m/z (%) =
344 (32) [M]+, 342 (52) [M – H2]+, 238 (100) [M – CH2C6H4-
CH3]+, 119 (48) [CH3C6H4CH2CH2]+. HRMS (EI): calcd. for
C25H27N [M – 2 H]+ 341.2138; found 341.2125.
(Phenethyl)propylamine (3n): Purification by column chromatog-
raphy on silica gel (CH2Cl2/MeOH, 95:5 + a few drops of Et3N, Rf
= 0.1). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.21–7.15 (m, 2
(4-Methoxybenzyl)bis[2-(p-tolyl)ethyl]amine (4d): Purification by
column chromatography on silica gel (CH2Cl2/MeOH, 95:5 + a few
drops of Et3N, Rf = 0.79). Isolated yield: 19% (based on the amine
H, aryl-H), 7.11–7.08 (m,
PhCH2CH2NH), 2.70 (m, 2 H, PhCH2CH2NH), 2.48 (t, JH,H
7.3 Hz, H, NHCH2CH2CH3), 1.43–1.33 (m,
3
H, aryl-H), 2.77 (m,
2
H, for Table 2, Entry 5). 1H NMR (300 MHz, CDCl3, 25 °C): δ = 7.20
3
3
=
(d, JH,H = 8.6 Hz, 2 H, aryl-H), 7.09–7.01 (m, 8 H, aryl-H), 6.82
2
2
H, (d, 3JH,H = 8.7 Hz, 2 H, aryl-H), 3.80 (s, 3 H, OCH3), 3.67 (s, 2 H,
NHCH2CH2CH3), 1.00 (br. s, 1 H, NH), 0.78 (t, 3JH,H = 7.4 Hz, 3 NCH2Ar), 2.75 (s, 8 H, ArCH2CH2N), 2.32 (s, 6 H, CH3C6H4)
H, NHCH2CH2CH3) ppm. 13C{1H} NMR (100.6 MHz, CDCl3, ppm. 13C{1H} NMR (75.5 MHz, CDCl3, 25 °C): δ = 158.5, 137.5,
25 °C): δ = 140.2, 128.7, 128.4, 126.1 (aryl), 51.8 (CH2NH), 51.2
(CH2NH), 36.5 (PhCH2), 23.2 (NHCH2CH2CH3), 11.8
135.3, 131.4, 129.9, 129.0, 128.6, 113.5 (aryl), 57.7 (NCH2Ar), 55.6
(ArCH2CH2N), 55.2 (OCH3), 33.0 (ArCH2CH2N), 21.0 (CH3)
Eur. J. Org. Chem. 2007, 3311–3325
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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