γ-Oxo γ-Aryl and γ-Aryl α-Amino Acids
(493 mg, 93%); m.p. 78–80 °C. IR (KBr): ν = 3374, 1686,
oil (519 mg, 88%). IR (thin film): ν = 3361, 2926, 1685, 1247 cm–1.
˜
˜
1
1516 cm–1. H NMR (CDCl3, 500 MHz): δ = 7.27 (m, 2 H), 7.18 1H NMR (CDCl3, 500 MHz): δ = 7.08 (m, 2 H), 6.81 (m, 2 H),
(m, 3 H), 4.69 (br., 1 H), 3.66 (m, 2 H), 3.56 (m, 1 H), 2.68 (m, 2 4.72 (br. s, 1 H), 3.76 (s, 3 H), 3.64 (m, 2 H), 3.54 (m, 1 H), 2.618
H), 1.78 (m, 2 H), 1.44 (s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): (m, 2 H), 1.73 (m, 2 H), 1.44 (s, 9 H) ppm. 13C NMR (CDCl3,
δ = 156.5, 141.5, 128.5, 128.3, 126.1, 79.7, 65.9, 52.5, 33.3, 32.4,
28.4 ppm. HRMS (ESI): m/z calcd. for C15H23NO3 [M + Na+]
288.1576; found 288.1574.
125 MHz): δ = 157.8, 156.6, 133.5, 129.2, 113.9, 79.8, 65.9, 55.3,
52.3, 33.5, 31.4, 28.4 ppm. HRMS (ESI): m/z calcd. for C16H25NO4
[M + Na+] 318.1681; found 318.1684.
2-(tert-Butyloxycarbonylamino)-3-(2-p-tolyl-1,3-dithian-2-yl)- 2-Boc-amino-3-[2-(3,4-dimethoxyphenyl)-1,3-dithian-2-yl]propan-1-
propan-1-ol (4b): Column chromatography (petroleum ether/ ol (4e): Column chromatography (petroleum ether/EtOAc, 6:4);
EtOAc, 4:1); colorless oil (636 mg, 83%). IR (thin film): ν = 3360, white solid (746 mg, 87%); m.p. 85–87 °C. IR (KBr): ν = 3380,
˜
˜
1
2981, 1690, 1160 cm–1. H NMR (CDCl3, 500 MHz): δ = 7.76 (d, 2932, 1691, 1510 cm–1. 1H NMR (CDCl3, 500 MHz): δ = 7.46 (dd,
J = 8.4 Hz, 2 H), 7.17 (d, J = 8.3 Hz, 2 H), 3.61 (m, 1 H), 3.41 J1 = 9.1, J2 = 2.45 Hz, 1 H), 7.44 (d, J = 2.45 Hz, 1 H), 6.85 (d, J
(dd, J1 = 11.02, J2 = 3.5 Hz, 1 H), 3.36 (dd, J1 = 10.87, J2 = 5.0 Hz,
= 9.0 Hz, 1 H), 4.39 (br., 1 H), 3.88 (s, 3 H), 3.87 (s, 3 H), 3.64 (m,
1 H), 2.70 (m, 4 H), 2.33 (s, 3 H), 2.25 (m, 2 H), 1.92 (m, 2 H), 1.3
1 H), 3.41 (dd, J1 = 11.6, J2 = 4.2 Hz, 1 H), 3.37 (dd, J1 = 11.1, J2
(s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 155.5, 138.1, = 5.1 Hz, 1 H), 2.70 (m, 4 H), 2.23 (m, 2 H), 1.93 (m, 2 H), 1.35
137.0, 129.6, 128.4, 79.5, 66.4, 57.0, 49.8, 45.8, 28.4, 27.7, 27.5,
25.0, 21.0 ppm. HRMS (ESI): m/z calcd. for C19H29NO3S2 [M +
Na+] 406.1487; found 406.1485.
(s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 155.9, 149.0,
148.1, 133.4, 121.1, 111.7, 110.9, 79.6, 66.6, 57.2, 56.0, 55.8, 49.8,
46.1, 28.3, 27.8, 27.6, 25.0 ppm. HRMS (ESI): m/z calcd. for
C20H31NO5S2 [M + Na+] 452.154; found 452.1548.
2-(tert-Butyloxycarbonylamino)-4-p-tolylbutan-1-ol (8b): Column
chromatography (petroleum ether/EtOAc, 8:2); white solid 2-(tert-Butyloxycarbonylamino)-4-(3,4-dimethoxyphenyl)butan-1-ol
(430 mg, 77%); m.p. 80–82 °C. IR (thin film): ν = 3383, 2925, 1688, (8e): Column chromatography (petroleum ether/EtOAc, 7:3); clear
1170 cm–1. 1H NMR (CDCl3, 500 MHz): δ = 7.06 (m, 4 H), 4.7 oil (565 mg, 87%). IR (thin film): ν = 3360, 2927, 1687, 1516 cm–1.
˜
˜
(br., 1 H), 3.64 (m, 2 H), 3.54 (m, 1 H), 2.63 (m, 2 H), 2.30 (s, 3
1H NMR (CDCl3, 500 MHz): δ = 6.74 (m, 3 H), 3.85 (s, 3 H), 3.83
H), 1.75 (m, 2 H), 1.44 (s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): (s, 3 H), 3.67 (m, 2 H), 3.54 (m, 1 H), 2.61 (m, 2 H), 1.75 (m, 2
δ = 156.6, 138.4, 129.2, 128.3, 79.7, 66.0, 52.6, 33.4, 32.2, 28.4,
21.0 ppm. HRMS (ESI): m/z calcd. for C16H25NO3 [M + H+]
280.1913; found 280.1918.
H), 1.44 (s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 156.3,
148.08, 147.1, 133.9, 120.1, 111.7, 79.7, 66.0, 56.0, 55.9, 52.4, 33.5,
32.0, 28.4 ppm. HRMS (ESI): m/z calcd. for C17H27NO5 [M + Na+]
348.1787; found 348.1780.
2-(tert-Butyloxycarbonylamino)-3-[2-(4-isopropylphenyl)-1,3-di-
thian-2-yl]propan-1-ol (4c): Column chromatography (petroleum
2-(tert-Butyloxycarbonylamino)-3-[2-(4-fluorophenyl)-1,3-dithian-
2-yl]propan-1-ol (4f): Column chromatography (petroleum ether/
EtOAc, 7.5:2.5); white solid (619 mg, 80%); m.p. 88–90 °C. IR
ether/EtOAc, 4:1); solid (700 mg, 85%); m.p. 96–98 °C. IR (KBr):
1
ν = 3395, 2960, 1691, 1170 cm–1. H NMR (CDCl , 400 MHz): δ
˜
3
= 7.72 (d, J = 8.2 Hz, 2 H), 7.16 (d, J = 8.2 Hz, 2 H), 4.40 (m, 1
(KBr): ν = 3412, 3270, 1675, 1157 cm–1 1H NMR (CDCl3,
.
˜
H), 3.32 (m, 2 H), 2.84 (m, 1 H), 2.6 (m, 4 H), 2.1 (m, 2 H), 1.87
500 MHz): δ = 7.88 (m, 2 H), 7.04 (m, 2 H), 4.37 (br. s, 1 H), 3.63
(m, 2 H), 1.3 (s, 9 H), 1.18 (d, J = 11.6 Hz, 6 H) ppm. 13C NMR (m, 1 H), 3.43 (dd, J1 = 11.6, J2 = 4.2 Hz, 1 H), 3.38 (dd, J1
=
(CDCl3, 125 MHz): δ = 155.5, 147.9, 138.5, 128.4, 126.9, 79.6, 66.4,
57.0, 49.9, 45.6, 33.6, 28.4, 27.4, 27.6, 25.0, 24.0, 23.9 ppm. HRMS
(ESI): m/z calcd. for C21H33NO3S2 [M + H+] 412.1980; found
412.1987.
11.0, J2 = 5.1 Hz, 1 H), 2.68 (m, 4 H), 2.23 (m, 2 H), 1.93 (m, 2
H), 1.36 (s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 162.8,
160.9, 155.7, 137.0, 130.6, 130.6, 115.7, 115.5, 79.7, 66.5, 56.7, 49.5,
46.2, 28.7, 27.7, 24.8 ppm. HRMS (ESI): m/z calcd. for
C18H26FNO3S2 [M + Na+] 410.1234; found 410.1236.
2-(tert-Butyloxycarbonylamino)-4-(4-isopropylphenyl)butan-1-ol
(8c): Column chromatography (petroleum ether/EtOAc, 8:2); clear
2-(tert-Butyloxycarbonylamino)-4-(4-fluorophenyl)butan-1-ol (8f):
oil (497 mg, 81%). IR (thin film): ν = 3362, 2959, 2926, 1687 cm–1.
Column chromatography (petroleum ether/EtOAc, 7:3); clear oil
˜
1H NMR (CDCl3, 500 MHz): δ = 7.12 (m, 4 H), 3.67 (m, 2 H),
3.55 (m, 1 H), 2.85 (s, 1 H), 2.63 (m, 2 H), 1.77 (m, 2 H), 1.44 (s,
9 H), 1.22 (m, 6 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 156.5,
146.6, 138.5, 128.2, 126.3, 79.6, 60.2, 52.5, 33.6, 33.3, 31.9, 28.3,
24.1 ppm. HRMS (ESI): m/z calcd. for C18H29NO3 [M + Na+]
330.2045; found 330.2046.
(537 mg, 95%). IR (thin film): ν = 3357, 1687, 1510, 1169 cm–1. 1H
˜
NMR (CDCl3, 500 MHz): δ = 7.10 (m, 2 H), 6.93 (m, 2 H), 4.86
(br. s, 1 H), 3.60 (m, 2 H), 3.51 (m, 1 H), 2.62 (m, 2 H), 1.72 (m,
2 H), 1.42 (s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 162.3,
160.4, 156.5, 137.2, 129.8, 115.3, 79.7, 65.5, 52.3, 33.5, 31.6,
28.4 ppm. HRMS (ESI): m/z calcd. for C15H22FNO3 [M + Na+]
306.1481; found 306.1479.
2-(tert-Butyloxycarbonylamino)-3-[2-(4-methoxyphenyl)-1,3-di-
thian-2-yl]propan-1-ol (4d): Column chromatography (petroleum
2-(tert-Butyloxycarbonylamino)-3-[2-(3-chlorophenyl)-1,3-dithian-
ether/EtOAc, 4:1); colorless oil (678 mg, 85%). IR (thin film): ν = 2-yl]propan-1-ol (4g): Column chromatography (petroleum ether/
˜
3382, 2932, 1691, 1510 cm–1. 1H NMR (CDCl3, 500 MHz): δ =
7.75 (d, J = 9.05 Hz, 2 H), 6.84 (d, J = 9.05 Hz, 2 H), 3.76 (s, 3
H), 3.57 (m, 1 H), 3.37 (dd, J1 = 22, J2 = 4.3 Hz, 1 H), 3.31 (dd,
J1 = 22.9, J2 = 5.0 Hz, 1 H), 2.65 (m, 4 H), 2.24 (dd, J1 = 14.6, J2
EtOAc, 7.5:2.5); colorless oil (693 mg, 86%). IR (thin film): ν =
˜
3399, 2976, 1808, 1689, 1368 cm–1. 1H NMR (CDCl3, 500 MHz):
δ = 7.92 (s, 1 H), 7.81 (d, J = 6 Hz, 1 H), 7.31 (m, 1 H), 7.24 (m,
1 H), 4.49 (br. s, 1 H), 3.64 (m, 1 H), 3.4 (m, 2 H), 2.66 (m, 4 H),
= 4.0 Hz, 1 H), 2.17 (dd, J1 = 15.0, J2 = 4.0 Hz, 1 H), 1.87 (m, 2 2.33 (m, 2 H), 1.93 (m, 2 H), 1.37 (s, 9 H) ppm. 13C NMR (CDCl3,
H), 1.32 (s, 9 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 158.6,
155.9, 132.9, 129.8, 114.1, 79.6, 66.5, 56.8, 55.4, 49.8, 46.05, 28.4,
27.7, 27.5, 25.0 ppm. HRMS (ESI): m/z calcd. for C19H29NO4S2
[M + Na+] 422.1436; found 422.1437.
125 MHz): δ = 155.7, 143.9, 134.8, 130.1, 128.9, 127.6, 127.0, 79.7,
66.6, 56.8, 49.5, 46.1, 28.4, 27.8, 27.6, 24.7 ppm. HRMS (ESI): m/z
calcd. for C18H26ClNO3S2 [M + Na+]: 426.0945, found 426.0940.
2-(tert-Butyloxycarbonylamino)-4-(4-chlorophenyl)butan-1-ol (8g):
2-(tert-Butyloxycarbonylamino)-4-(4-methoxyphenyl)butan-1-ol Column chromatography (petroleum ether/EtOAc, 75:25); clear oil
(8d): Column chromatography (petroleum ether/EtOAc, 8:2); clear
(568 mg, 95%). IR (thin film): ν = 3346, 2976, 1686, 1170 cm–1. 1H
˜
Eur. J. Org. Chem. 2012, 7120–7128
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7125