C. Xu, Y. Zhang, C. Yuan
FULL PAPER
(7.58) [Mϩ], 179 (15.56), 167 (34.17), 138 (58.41), 127 (39.82), 111
5.67 (dd, J ϭ 6.9, 7.5 Hz, 0.5 H, ArCH), 5.21 (dd, J ϭ 6.0, 6.3 Hz,
(90.29), 138 (35.45), 99 (73.88), 81 (87.57), 65 (43.58), 43 (100.00). 0.5 H, ArCH), 4.53 (d, J ϭ 14.7 Hz, 0.5 H, OCHCO), 4.38 (d, J ϭ
C9H17O5P (236.20): calcd. C 45.77, H 7.25; found C 45.72, H 7.35.
13.8 Hz, 0.5 H, OCHCO), 4.31Ϫ4.20 (m, 4 H, OCH2CH3), 3.02
(dd, J ϭ 6.8, 18.3 Hz, 0.5 H, CHCH2CO), 2.84Ϫ2.77 (m, 1 H,
CHCH2CO), 2.70Ϫ2.57 (m, ArCH2CH3, 2.5 H, CHCH2CO),
1.41Ϫ1.32 (m, 6 H, OCH2CH3), 1.24 (t, J ϭ 7.5 Hz, 3 H,
ArCH2CH3) ppm. 31P NMR (120 MHz, CDCl3): δ ϭ 14.26,
13.47 ppm. EI-MS: m/z ϭ 326 (10.09) [Mϩ], 256 (4.65), 188 (41.93),
179 (18.16), 151 (12.07), 133 (100.00), 132 (80.17), 117 (54.39), 105
(23.05), 91 (26.64), 65 (13.72). C16H23O5P (326.33): calcd. C 58.90,
H 7.10; found C 58.79, H 7.19.
(5S)-2-Diethoxyphosphoryl-5-ethyl-3-oxotetrahydrofuran (3b): Col-
orless oil; yield: 94%. [α]2D5 ϭ ϩ14.5 (c ϭ 2.1, CHCl3). IR (film):
ν˜ ϭ 2980, 2937, 2883, 1763, 1255, 1050, 1024, 974 cmϪ1. 1H NMR
(300 MHz, CDCl3): δ ϭ 4.63Ϫ4.58 (m, 0.5 H), 4.36 (d, J ϭ
14.4 Hz, 0.5 H, OCHCO), 4.29Ϫ4.18 (m, 5 H, OCH2CH3,
OCHCH2, OCHCO), 2.76Ϫ2.55 (m, 1 H, CHCH2CO), 2.44Ϫ2.22
(m, 1 H, CHCH2CO), 1.90Ϫ1.67 (m, 2 H, CHCH2CH3), 1.40Ϫ1.34
(m, 6 H, OCH2CH3), 1.05Ϫ0.97 (m, 3 H, CHCH2CH3) ppm. 31P
NMR (120 MHz, CDCl3): δ ϭ 17.17, 16.34 ppm. EI-MS: m/z ϭ
250 (6.97) [Mϩ], 221 (11.57), 179 (23.15), 167 (80.49), 139 (50.49),
127 (42.92), 111 (100.00), 99 (57.57), 81 (85.61), 65 (65.79), 41
(79.70). C10H19O5P (250.23): calcd. C 48.00, H 7.65; found C 48.15,
H 7.94.
(5R)-2-Diethoxyphosphoryl-5-(4-methoxyphenyl)-3-oxotetra-
hydrofuran (3g): Colorless oil; yield: 96%. [α]2D5 ϭ ϩ64.0 (c ϭ 0.8,
CHCl3). IR (film): ν˜ ϭ 2985, 2935, 2913, 2841, 1761, 1517, 1251,
1027, 977 cmϪ1 1H NMR (300 MHz, CDCl3): δ ϭ 7.43 (d, J ϭ
.
8.7 Hz, 1 H, ArH), 7.32 (d, J ϭ 9.0 Hz, 1 H, ArH), 6.93 (dd, J ϭ
2.1, 8.7 Hz, 2 H, ArH), 5.65 (dd, J ϭ 6.6, 6.9 Hz, 0.5 H, ArCH),
5.19 (dd, J ϭ 6.3, 6.6 Hz, 0.5 H, ArCH), 4.52 (d, J ϭ 14.7 Hz, 0.5
H, OCHCO), 4.37 (d, J ϭ 13.8 Hz, 0.5 H, OCHCO), 4.30Ϫ4.20
(m, 4 H, OCH2CH3), 3.82 (s, 3 H, OCH3), 3.00 (dd, J ϭ 6.8,
18.3 Hz, 0.5 H, CHCH2CO), 2.83Ϫ2.76 (m, 1 H, CHCH2CO), 2.64
(dd, J ϭ 6.6, 18.3 Hz, 0.5 H, CHCH2CO), 1.44Ϫ1.26 (m, 6 H,
OCH2CH3) ppm. 31P NMR (120 MHz, CDCl3): δ ϭ 3.93,
8.59 ppm. EI-MS: m/z ϭ 328 (22.97) [Mϩ], 258 (3.11), 191 (22.27),
190 (23.03), 179 (10.03), 150 (15.57), 135 (100.00), 134 (54.28),
121(33.01), 91 (18.39). C15H21O6P (328.30): calcd. C 54.88, H 6.45;
found C 54.58, H 6.74.
(5R)-2-Diethoxyphosphoryl-3-oxo-5-vinyltetrahydrofuran (3c): Col-
orless oil; yield: 95%. [α]2D5 ϭ ϩ21.2 (c ϭ 1.0, CHCl3). IR (film):
ν˜ ϭ 2897, 2914, 1761, 1254, 1048, 1023, 975 cmϪ1 1H NMR
.
(300 MHz, CDCl3): δ ϭ 6.12Ϫ5.87 (m, 1 H, CHϭCH2), 5.44Ϫ5.27
(m, 2 H, CH2ϭCH), 5.18Ϫ5.09 (m, 0.5 H, OCHCH2), 4.80Ϫ4.50
(m, 0.5 H, OCHCH2), 4.38 (d, J ϭ 14.4 Hz, 0.5 H, OCHCO),
4.30Ϫ4.20 (m, 4.5 H, OCH2CH3, OCHCO), 2.88Ϫ2.37 (m, 2 H,
CHCH2CO), 1.40Ϫ1.34 (m, 6 H, OCH2CH3) ppm. 31P NMR
(120 MHz, CDCl3): δ ϭ 16.81, 15.99 ppm. EI-MS: m/z ϭ 248
(4.77) [Mϩ], 220 (13.18), 179 (23.47), 167 (74.60), 139 (59.01), 111
(100.00), 99 (54.38), 81 (59.43), 65 (50.03), 54 (76.59). C10H17O5P
(248.21): calcd. C 48.39, H 6.90; found C 48.10, H7.20.
(5R)-2-Diethoxyphosphoryl-5-(2-furyl)-3-oxotetrahydrofuran (3h):
Colorless oil; yield: 97%. [α]2D5 ϭ Ϫ6.0 (c ϭ 0.8, CHCl3). IR (film):
(5R)-2-Diethoxyphosphoryl-3-oxo-5-phenyltetrahydrofuran
Colorless oil; yield: 96%. [α]2D5 ϭ ϩ66.3 (c ϭ 1.5, CHCl3). IR (film):
ν˜ ϭ 2986, 2914, 1763, 1252, 1048, 1023, 977 cmϪ1 1H NMR
(3d):
1
ν˜ ϭ 2987, 1763, 1253, 1046, 1021, 977 cmϪ1. H NMR (300 MHz,
CDCl3): δ ϭ 7.46Ϫ7.28 (m, 1 H, ArH), 6.49Ϫ6.37 (m, 2 H, ArH),
5.66 (t, J ϭ 7.4 Hz, 0.5 H, ArCH), 5.28 (dd, J ϭ 6.0, 6.3 Hz, 0.5
H, ArCH), 4.45 (t, J ϭ 13.8 Hz, 0.5 H, OCHCO), 4.36 (d, J ϭ
13.5 Hz, 0.5 H, OCHCO), 4.29Ϫ4.18 (m, 4 H, OCH2CH3),
3.16Ϫ2.75 (m, 2 H, CHCH2CO), 1.41Ϫ1.31 (m, 6 H, OCH2CH3)
ppm. 31P NMR (120 MHz, CDCl3): δ ϭ 12.57, 12.46 ppm. EI-MS:
m/z ϭ 288 (7.96) [Mϩ], 218 (32.87), 179 (27.44), 151 (29.32), 123
(43.04), 109 (17.42), 95 (30.74), 94 (100.00), 81 (54.58), 65 (29.32).
C12H17O6P (288.23): calcd. C 50.00, H 5.94; found C 49.86, H 6.05.
.
(300 MHz, CDCl3): δ ϭ 7.52Ϫ7.28 (m, 5 H, ArH), 5.71 (dd, J ϭ
6.9, 6.9 Hz, 0.5 H, ArCH), 5.25 (dd, J ϭ 5.7, 6.0 Hz, 0.5 H, ArCH),
4.55 (d, J ϭ 14.1 Hz, 0.5 H, OCHCO), 4.40 (d, J ϭ 13.8 Hz, 0.5
H, OCHCO), 4.32Ϫ4.21 (m, 4 H, OCH2CH3), 3.09Ϫ2.56 (m, 2
H, CHCH2CO), 1.46Ϫ1.29 (m, 6 H, OCH2CH3) ppm. 31P NMR
(120 MHz, CDCl3): δ ϭ 14.24, 13.45 ppm. 13C NMR (75.5 MHz,
CDCl3): δ ϭ 208.5 (J ϭ 39.4 Hz), 139.7 (J ϭ 17.7 Hz), 128.8, 126.4,
126.1, 80.1 (J ϭ 10.4 Hz), 79.3 (J ϭ 19.3 Hz), 63.7 (J ϭ 13.4 Hz),
45.1 (J ϭ 74.9 Hz), 16.5 ppm. EI-MS: m/z ϭ 298 (1.35) [Mϩ], 242
(3.48), 179 (20.94), 160 (32.23), 144 (30.04), 123 (18.21), 105
(89.00), 104 (100.00), 77 (30.67). C14H19O5P (298.27): calcd. C
56.38, H 6.42; found C 56.10, H 6.62.
(5R)-5-(2-Bromophenyl)-2-diethoxyphosphoryl-3-oxotetrahydrofuran
(3i): Colorless oil; yield: 95%. [α]2D5 ϭ ϩ87.4 (c ϭ 0.8, CHCl3). IR
(film): ν˜ ϭ 2985, 2932, 2912, 1763, 1254, 1047, 1021, 976 cmϪ1. 1H
NMR (300 MHz, CDCl3): δ ϭ 7.84 (d, J ϭ 8.4 Hz, 1 H, ArH),
7.60Ϫ7.53 (m, 1.5 H, ArH), 7.42Ϫ7.35 (m, 1 H, ArH), 7.24Ϫ7.20
(m, 1 H, ArH), 5.93 (t, J ϭ 8.1 Hz, 0.5 H, ArCH), 5.58 (dd, J ϭ
5.4, 5.7 Hz, 0.5 H, ArCH), 4.63 (d, J ϭ 14.4 Hz, 0.5 H, OCHCO),
4.43 (d, J ϭ 14.7 Hz, 0.5 H, OCHCO), 4.33Ϫ4.23 (m, 4 H,
OCH2CH3), 3.31 (dd, J ϭ 6.9, 18.6 Hz, 0.5 H, CHCH2CO), 3.13
(dd, J ϭ 6.0, 18.6 Hz, 0.5 H, CHCH2CO), 2.51Ϫ2.37 (m, 1 H,
CHCH2CO), 1.43Ϫ1.36 (m, 6 H, OCH2CH3) ppm. 31P NMR
(120 MHz, CDCl3): δ ϭ 14.21, 13.34 ppm. EI-MS: m/z ϭ 377
(0.84) [Mϩ], 348 (11.56), 306 (14.13), 297 (88.21), 269 (25.33), 241
(22.23), 184 (68.51), 167 (62.78), 123 (36.20), 111 (49.96), 103
(100.00), 77 (80.38), 65 (35.96). C14H18BrO5P (377.17): calcd. C
44.58, H 4.81; found C 44.79, H 4.75.
(5R)-2-Diethoxyphosphoryl-5-(4-methylphenyl)-3-oxotetra-
hydrofuran (3e): Colorless oil; yield: 97%. [α]2D5 ϭ ϩ64.3 (c ϭ 1.1,
CHCl3). IR (film): ν˜ ϭ 2985, 2916, 1761, 1251, 1048, 1023, 977
cmϪ1. 1H NMR (300 MHz, CDCl3): δ ϭ 7.81Ϫ7.22 (m, 4 H, ArH),
5.66 (dd, J ϭ 6.9, 8.6 Hz, 0.5 H, ArCH), 5.19 (dd, J ϭ 5.1, 6.0 Hz,
0.5 H, ArCH), 4.50 (d, J ϭ 14.4 Hz, 0.5 H, OCHCO), 4.36 (d,
J ϭ 13.9 Hz, 0.5 H, OCHCO), 4.26Ϫ4.21 (m, 4 H, OCH2CH3),
3.03Ϫ2.03 (m, 2 H, CHCH2CO), 2.40 (s, 3 H, ArCH3), 1.39Ϫ1.24
(m, 6 H, OCH2CH3) ppm. 31P NMR (120 MHz, CDCl3): δ ϭ
18.23, 17.38 ppm. EI-MS: m/z ϭ 312 (4.65) [Mϩ], 179 (20.13), 174
(37.94), 158 (17.23), 119 (100.00), 118 (70.45), 105 (19.48), 91
(52.37). HR-MS Calcd. for C15H21O5PNa ([M ϩ Na]ϩ): 335.1024;
found 335.1019.
(5R)-2-Diethoxyphosphoryl-5-(4-fluorophenyl)-3-oxotetrahydrofuran
(3j): Colorless oil; yield: 96%. [α]2D5 ϭ ϩ71.9 (c ϭ 1.3, CHCl3). IR
(film): ν˜ ϭ 2987, 2914, 1762, 1514, 1252, 1048, 1023, 977 cmϪ1. 1H
NMR (300 MHz, CDCl3): δ ϭ 7.53Ϫ7.48 (m, 1 H, ArH),
(5R)-2-Diethoxyphosphoryl-5-(4-ethylphenyl)-3-oxotetrahydrofuran
(3f): Colorless oil; yield: 93%. [α]2D5 ϭ ϩ66.5 (c ϭ 1.1, CHCl3). IR
(film): ν˜ ϭ 2969, 2933, 2914, 2875, 1761, 1253, 1048, 1022, 976
cmϪ1. 1H NMR (300 MHz, CDCl3): δ ϭ 7.43 (d, J ϭ 8.4 Hz, 1 H, 7.41Ϫ7.37 (m, 1 H, ArH), 7.13Ϫ7.07 (m, 2 H, ArH), 5.70 (dd, J ϭ
ArH), 7.31 (d, J ϭ 8.4 Hz, 1 H, ArH), 7.27Ϫ7.21 (m, 2 H, ArH), 6.9, 6.9 Hz, 0.5 H, ArCH), 5.25 (dd, J ϭ 6.0, 6.0 Hz, 0.5 H, ArCH),
2258
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2004, 2253Ϫ2262