Job/Unit: O30947
/KAP1
Date: 02-09-13 17:45:07
Pages: 12
H. Zhu et al.
FULL PAPER
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 7.27–7.15 (m, 3 H),
7.14–7.08 (m, 2 H), 6.97–6.91 (m, 2 H), 6.70–6.64 (m, 2 H), 6.41
(d, J = 9.5 Hz, 1 H), 5.87 (d, J = 9.5 Hz, 1 H), 4.90 (dd, J = 8.7,
4.0 Hz, 1 H), 4.61 (t, J = 8.7 Hz, 1 H), 4.14 (dd, J = 8.7, 4.0 Hz, 1
H), 2.38 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 157.1,
138.2, 137.0, 132.6, 128.9, 128.6, 128.5, 126.2, 121.7, 117.0, 70.2,
58.7, 21.2 ppm. MS (EI, 70 eV): m/z (%) = 279 (98.20) [M+], 280
1428, 1401, 1341, 1237, 1213, 1106, 1075, 861 cm–1. C17H14N2O4
(310.31): calcd. C 65.80, H 4.55, N 9.03; found C 65.75, H 4.33, N
8.78.
(S)-4-Benzyl-3-[(Z)-2-phenylethenyl]oxazolidin-2-one [(Z)-2l]: Pre-
pared according to Typical Procedure II. The reaction of CuCl
(3.0 mg, 0.03 mmol), PPh3 (9.9 mg, 0.036 mmol), tBuONa (4.2 mg,
0.045 mmol), 1l (83.0 mg, 0.3 mmol), B2pin2 (84.5 mg, 0.33 mmol),
and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at room temp.
for 6 h, afforded (Z)-2l (73.5 mg, 88%) as a white solid, m.p. 108–
109 °C (n-hexane/EtOAc). [α]2D0 = –177.5 (c = 1.01, CH2Cl2). 1H
NMR (400 MHz, CDCl3): δ = 7.46–7.36 (m, 3 H), 7.36–7.30 (m, 2
H), 7.17–7.09 (m, 3 H), 6.64 (d, J = 9.8 Hz, 1 H), 6.48–6.40 (m, 2
H), 6.11 (d, J = 9.8 Hz, 1 H), 4.20–4.00 (m, 3 H), 2.86–2.76 (m, 1
H), 2.25 (dd, J = 13.2, 10.0 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 156.6, 135.8, 135.2, 129.3, 129.0, 128.6, 128.4, 127.4,
126.9, 122.3, 114.2, 66.0, 55.5, 36.6 ppm. MS (EI, 70 eV): m/z (%)
(24.77) [M+ + 1], 144 (100). IR (KBr): ν = 3043, 2990, 2923, 1763,
˜
1678, 1600, 1478, 1424, 1355, 1270, 1238, 1077, 1043, 956,
886 cm–1. C18H17NO2 (279.34): calcd. C 77.40, H 6.13, N 5.01;
found C 77.32, H 5.91, N 4.76.
(S)-4-Phenyl-3-[(Z)-2-(4-methoxylphenyl)ethenyl]oxazolidin-2-one
[(Z)-2i]: Prepared according to Typical Procedure II. The reaction
of CuCl (3.1 mg, 0.03 mmol), PPh3 (9.3 mg, 0.036 mmol), tBuONa
(4.5 mg, 0.045 mmol), 1i (87.7 mg, 0.3 mmol), B2pin2 (83.6 mg,
0.33 mmol), and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at
room temp. for 24 h, afforded (Z)-2i (58.2 mg, 68%) as a white
solid, m.p. 86–87 °C (n-hexane/Et2O). [α]2D0 = –164.3 (c = 1.02,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 7.27–7.17 (m, 3 H),
7.00–6.96 (m, 2 H), 6.86–6.81 (m, 2 H), 6.72–6.68 (m, 2 H), 6.36
(d, J = 9.4 Hz, 1 H), 5.85 (d, J = 9.4 Hz, 1 H), 4.91 (dd, J = 8.6,
4.1 Hz, 1 H), 4.62 (t, J = 6.8 Hz, 1 H), 4.14 (dd, J = 8.6, 4.1 Hz, 1
H), 3.85 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.7,
157.1, 138.2, 130.2, 128.7, 128.5, 127.9, 126.1, 121.2, 117.0, 113.4,
58.8, 55.3 ppm. MS (EI, 70 eV): m/z (%) = 295 (100) [M+], 296
= 279 (44.64) [M+], 280 (8.92) [M+ + 1], 144 (100). IR (KBr): ν =
˜
3060, 2985, 2928, 1760, 1649, 1485, 1447, 1409, 1233, 1084,
1013 cm–1. C18H17NO2 (279.34): calcd. C 77.40, H 6.13, N 5.01;
found C 77.15, H 6.43, N 4.85.
(S)-4-Benzyl-3-[(Z)-2-(4-methylphenyl)ethenyl]oxazolidin-2-one
[(Z)-2m]: Prepared according to Typical Procedure II. The reaction
of CuCl (3.4 mg, 0.03 mmol), PPh3 (9.5 mg, 0.036 mmol), tBuONa
(4.4 mg, 0.045 mmol), 1m (87.3 mg, 0.3 mmol), B2pin2 (84.7 mg,
0.33 mmol), and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at
room temp. for 6 h, afforded (Z)-2m (72.9 mg, 83%) as a white
solid, m.p. 111–112 °C (n-hexane/EtOAc). [α]2D0 = –179.2 (c = 1.02,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 7.25–7.19 (m, 4 H),
7.17–7.10 (m, 3 H), 6.59 (d, J = 9.7 Hz, 1 H), 6.49–6.43 (m, 2 H),
6.08 (d, J = 9.7 Hz, 1 H), 4.19–4.01 (m, 3 H), 2.80 (dd, J = 13.1,
3.0 Hz, 1 H), 2.43 (s, 3 H), 2.25 (dd, J = 13.2, 10.0 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 156.7, 137.3, 135.4, 132.8, 129.2,
129.1, 129.0, 128.6, 126.9, 121.9, 114.4, 66.0, 55.5, 36.6, 21.2 ppm.
MS (EI, 70 eV): m/z (%) = 293 (41.94) [M+], 294 (9.88) [M+ + 1],
(27.94) [M+ + 1]. IR (neat): ν = 2946, 2910, 2834, 1748, 1649,
˜
1605, 1511, 1394, 1321, 1246, 1206, 1073, 1034, 1021, 843 cm–1.
C18H17NO3 (295.34): calcd. C 73.20, H 5.80, N 4.74; found C
72.90, H 5.71, N 4.42.
(S)-4-Phenyl-3-[(Z)-2-(4-acetylphenyl)ethenyl]oxazolidin-2-one [(Z)-
2j]: Prepared according to Typical Procedure II. The reaction of
CuCl (3.3 mg, 0.03 mmol), PPh3 (9.6 mg, 0.036 mmol), tBuONa
(4.7 mg, 0.045 mmol), 1j (91.6 mg, 0.3 mmol), B2pin2 (84.0 mg,
0.33 mmol), and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at
room temp. for 24 h, afforded (Z)-2j (73.4 mg, 80%) as a white
solid, m.p. 138–139 °C (n-hexane/EtOAc). [α]2D0 = –163.2 (c = 1.01,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 7.91–7.85 (m, 2 H),
7.28–7.21 (m, 1 H), 7.21–7.14 (m, 2 H), 7.12–7.06 (m, 2 H), 6.65–
6.55 (m, 3 H), 5.89 (d, J = 9.7 Hz, 1 H), 4.90 (dd, J = 8.7, 4.4 Hz,
1 H), 4.64 (t, J = 8.7 Hz, 1 H), 4.13 (dd, J = 8.7, 4.4 Hz, 1 H), 2.64
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 197.5, 156.8,
140.8, 137.5, 135.5, 129.2, 128.8, 128.6, 127.9, 125.9, 123.7, 114.7,
70.3, 58.9, 26.6 ppm. MS (EI, 70 eV): m/z (%) = 307 (10.01) [M+],
158 (100). IR (KBr): ν = 3025, 2973, 2922, 1743, 1652, 1474, 1449,
˜
1409, 1235, 1191, 1078, 997, 859 cm–1. C19H19NO2 (293.36): calcd.
C 77.79, H 6.53, N 4.77; found C 77.59, H 6.70, N 4.68.
(S)-4-Benzyl-3-[(Z)-2-(4-methoxylphenyl)ethenyl]oxazolidin-2-one
[(Z)-2n]: Prepared according to Typical Procedure II. The reaction
of CuCl (3.4 mg, 0.03 mmol), PPh3 (9.1 mg, 0.036 mmol), tBuONa
(4.3 mg, 0.045 mmol), 1n (93.8 mg, 0.3 mmol), B2pin2 (84.3 mg,
0.33 mmol), and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at
room temp. for 9 h, afforded (Z)-2n (79.7 mg, 85%) as a white so-
lid, m.p. 98–99 °C (n-hexane/EtOAc). [α]2D0 = –178.3 (c = 1.00,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 7.29–7.23 (m, 2 H),
7.21–7.13 (m, 3 H), 7.00–6.92 (m, 2 H), 6.57–6.49 (m, 3 H), 6.07
(d, J = 9.6 Hz, 1 H), 4.19–4.01 (m, 3 H), 3.87 (s, 3 H), 2.88–2.78
(m, 1 H), 2.29 (dd, J = 13.3, 9.8 Hz, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 159.0, 156.7, 135.4, 130.4, 129.1, 128.7,
127.9, 126.9, 121.5, 114.7, 113.8, 66.0, 55.6, 55.4, 36.7 ppm. MS
(EI, 70 eV): m/z (%) = 309 (58.20) [M+], 310 (13.67) [M+ + 1], 174
308 (15.61) [M+ + 1], 40 (100). IR (KBr): ν = 3119, 3030, 2994,
˜
1747, 1679, 1601, 1360, 1267, 1173, 1090, 1036 cm–1. C19H17NO3
(307.35): calcd. C 74.25, H 5.58, N 4.56; found C 74.08, H 5.71, N
4.31.
(S)-3-[(Z)-2-(4-Nitrophenyl)ethenyl]-4-phenyloxazolidin-2-one [(Z)-
2k]: Prepared according to Typical Procedure II. The reaction of
CuCl (3.2 mg, 0.03 mmol), PPh3 (9.5 mg, 0.036 mmol), tBuONa
(4.6 mg, 0.045 mmol), 1k (93.0 mg, 0.3 mmol), B2pin2 (83.3 mg,
0.33 mmol), and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at
room temp. for 3 h, afforded (Z)-2k (70.7 mg, 76%) as a yellow
solid, m.p. 151–152 °C (n-hexane/EtOAc). [α]2D0 = –166.5 (c = 1.02,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 8.16–8.07 (m, 2 H),
7.28–7.22 (m, 1 H), 7.22–7.15 (m, 2 H), 7.15–7.07 (m, 2 H), 6.68
(d, J = 9.8 Hz, 1 H), 6.65–6.60 (m, 2 H), 5.87 (d, J = 9.8 Hz, 1 H),
4.88 (dd, J = 8.7, 4.8 Hz, 1 H), 4.69 (t, J = 8.8 Hz, 1 H), 4.13 (dd,
J = 8.7, 4.8 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
156.6, 146.4, 142.7, 137.0, 129.6, 129.0, 128.8, 125.7, 124.7, 123.0,
113.0, 70.4, 59.2 ppm. MS (EI, 70 eV): m/z (%) = 310 (100) [M+].
(100). IR (KBr): ν = 3004, 2974, 2911, 1756, 1657, 1508, 1419,
˜
1399, 1252, 1230, 1178, 1076, 1021 cm–1. C19H19NO3 (309.36):
calcd. C 73.77, H 6.19, N 4.53; found C 73.93, H 6.10, N 4.39.
(S)-4-Benzyl-3-[(Z)-2-(4-acetylphenyl)ethenyl]oxazolidin-2-one [(Z)-
2o]: Prepared according to Typical Procedure II. The reaction of
CuCl (3.6 mg, 0.03 mmol), PPh3 (9.5 mg, 0.036 mmol), tBuONa
(4.5 mg, 0.045 mmol), 1o (94.3 mg, 0.3 mmol), B2pin2 (83.9 mg,
0.33 mmol), and MeOH (24 μL, 0.6 mmol) in toluene (1.0 mL) at
room temp. for 5 h, afforded (Z)-2o (73.8 mg, 78%) as a white so-
lid, m.p. 88–89 °C (n-hexane/EtOAc). [α]2D0 = –173.2 (c = 1.02,
IR (KBr): ν = 3104, 3034, 2968, 2910, 1770, 1651, 1594, 1512, CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 8.06–7.96 (m, 2 H),
˜
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