C. Yuan et al. / Tetrahedron 59 (2003) 6095–6102
6101
(4H, m, OCH2CH2CH3), 1.39 (3H, q, J¼16.2, 7.2 Hz,
CHCH3), 0.96–0.88 (6H, m, OCH2CH2CH3); m/z (EI) 343
(11 Mþ), 256 (5), 208 (7), 178 (10), 172 (4), 134 (27), 123
(6), 91 (100), 83 (7), 65 (7%).
7.35; N, 4.28. C10H22NO5P requires C, 54.71; H, 7.35; N,
4.25]; [a]2D0¼224.7 (c 0.70, CH3OH); nmax (liquid film)
3238, 3037, 2979, 2910, 1720, 1541, 1282, 1028, 970 cm21
;
dH(300 MHz, CDCl3) 7.36–7.27 (5H, m, C6H5), 5.17–5.07
(3H, m, NH, OCH2Ph), 4.16–3.96 (5H, m, OCH2CH3,
CHNH), 1.94–1.87 (1H, m, CHCH2CH3), 1.68–1.57 (1H,
m, CHCH2CH3), 1.63–1.23 (6H, m, OCH2CH3), 1.01 (3H,
t, J¼7.5 Hz, CHCH2CH3); m/z (EI) 329 (8, Mþ), 228 (7),
192 (7), 166 (2), 148 (37), 109 (5), 91 (100), 65 (7%).
4.3.28. (R)-Diisopropyl 1-aminoethanephosphonate
(7c).16 Colourless oil; [a]D20¼21.5 (c 0.85, CH3OH); nmax
(liquid film) 3375, 3296, 2980, 2935, 2876, 1386, 1375,
1238, 1110, 983 cm21; dH(300 MHz, CDCl3) 4.76–4.70
(2H, m, OCH(CH3)2), 3.07–3.02 (1H, m, CHNH2), 1.36–
1.30 (15H, m, OCH(CH3)2, CHCH3); m/z (EI) 209 (1 Mþ),
194 (5), 152 (8), 124 (11), 110 (19), 96 (35), 82 (16), 70
(43), 44 (100%).
4.3.34. (R)-Diethyl 1-(1-methoxy)acetylaminopropane-
phosphonate (10d). Colourless oil; [Found: C, 44.99; H,
8.12; N, 5.24. C10H22NO5P requires C, 44.94; H, 8.30; N,
5.24]; [a]2D0¼þ25.1 (c 0.90, CH3OH); nmax (liquid film)
3414, 3271, 2980, 2937, 1679, 1525, 1235, 1116, 1050,
1024, 971 cm21; dH(300 MHz, CDCl3) 6.62 (1H, d,
J¼10.2 Hz, NH), 4.41–4.34 (1H, m, CHNH), 4.19–4.08
(4H, m, OCH2CH3), 3.96–3.93 (2H, m, COCH2OCH3),
3.46 (3H, s, OCH3), 2.01–1.93 (1H, m, CHCH2CH3), 1.68–
1.61 (1H, m, CHCH2CH3), 1.39–1.26 (6H, m, OCH2CH3),
1.00 (3H, t, J¼7.5 Hz, CHCH2CH3); m/z (EI) 267 (1, Mþ),
222 (4), 194 (5), 166 (9), 130 (100), 122 (7), 105 (17), 70
(45), 58 (13), 45 (70%).
4.3.29. (S)-Diisopropyl 1-acetylaminoethanephospho-
nate (8c). Colourless oil; [Found: C, 47.53; H, 8.49; N,
5.38. C10H22NO4P requires C, 47.80; H, 8.83; N, 5.57];
[a]2D0¼þ55.3 (c 0.55, CH3OH); nmax (liquid film) 3264,
2983, 293.8, 2876, 2820, 1681, 1551, 1388, 1375, 1228,
985 cm21; dH(300 MHz, CDCl3) 6.30 (1H, d, J¼6.9 Hz,
NH), 4.74–4.68 (2H, m, OCH(CH3)2), 4.05–4.40 (1H, m,
CHCH3), 2.03 (3H, s, COCH3), 1.39–1.30 (15H, m,
OCH(CH3)2, CHCH3); m/z (EI) 251 (1, Mþ), 210 (3), 192
(2), 166 (8), 150 (26), 124 (52), 109 (11), 86 (36), 82 (20),
69 (18), 44 (100), 43 (64%).
4.3.35. Diethyl 1-amino-2,2,2-trifluoroethanephospho-
nate (7e).18 Colourless oil; nmax (liquid film) 3407, 3328,
2989, 2937, 1322, 1262, 1183, 1117, 1054, 1026, 977 cm21
;
dH(300 MHz, CDCl3) 4.30–4.20 (4H, m, OCH2CH3), 3.59
(1H, dq, J¼19.5, 8.4 Hz, CHNH2), 1.37 (6H, dt, J¼7.2,
0.6 Hz, OCH2CH3); m/z (EI) 235 (1, Mþ), 138 (22), 120
(11), 111 (20), 106 (100), 82 (20), 79 (38), 59 (18), 44
(18%).
4.3.30. (R)-Diisopropyl 1-benzyloxycarbonylamino-
ethanephosphonate (9c). Colourless oil; [Found: C,
55.74; H, 7.49; N, 3.93. C16H26NO5P requires C, 55.97;
H, 7.63; N, 4.08%]; [a]2D0¼218.9 (c 0.55, CH3OH); nmax
(liquid film) 3236, 3037, 2981, 2938, 2876, 1721, 1541,
1269, 1251, 1228, 1047, 990 cm21;dH(300 MHz, CDCl3)
7.36–7.26 (5H, m, C6H5), 5.11 (2H, s, OCH2Ph), 5.03 (1H,
d, J¼9.3 Hz, NH), 4.78–4.61 (2H, m, OCH(CH3)2), 4.13–
4.08 (1H, m, CHCH3), 1.36–1.24 (15H, m, OCH(CH3)2,
CHCH3); m/z (EI) 343 (7, Mþ), 301 (4), 256 (5), 242 (3),
208 (7), 178 (10), 166 (7), 134 (24), 124 (23), 91 (100), 82
(5), 65 (7%).
4.3.36. (R)-Dipropyl 1-aminopropanephosphonate (7f).
Colourless oil; [Found: C, 48.28; H, 9.63; N, 6.40.
C9H22NO3P requires C, 48.42; H, 9.93; N, 6.27];
[a]2D0¼21.9 (c 0.65, CH3OH); nmax (liquid film) 3484,
3379, 3303, 1968, 1939, 2896, 1465, 1236, 1068, 995 cm21
;
dH(300 MHz, CDCl3) 4.08–4.00 (4H, m, OCH2CH2CH3),
2.93–2.91 (1H, m, CHNH2), 1.97–1.82 (1H, m, CHCH2-
CH3), 1.75–1.65 (4H, m, OCH2CH2CH3), 1.60–1.53 (2H,
m, CHCH2CH3), 1.08 (3H, t, J¼7.2 Hz, CHCH2CH3),
0.99–0.94 (6H, m, OCH2CH2CH3); m/z (EI) 223 (1, Mþ),
152 (1), 110 (4), 83 (16), 82 (7), 65 (3), 58 (100), 43 (10%).
4.3.31. (R)-Diethyl 1-aminopropanephosphonate (7d).17
Colourless oil; [a]D20¼22.7 (c 1.10, CH3OH); nmax (liquid
film) 3468, 3382, 2982, 2910, 1393, 1231, 1056, 1027,
963 cm21; dH(300 MHz, CDCl3) 4.22–4.12 (4H, m,
OCH2CH3), 2.95–2.86 (1H, m, CHNH2), 1.95–1.85 (1H,
m, CHCH2CH3), 1.60–1.51 (1H, m, CHCH2CH3), 1.36
(6H, t, J¼7.2 Hz, OCH2CH3), 1.90 (3H, t, J¼7.5 Hz,
CHCH2CH3); m/z (EI) 195 (1, Mþ), 166 (2), 138 (4), 110
(7), 82 (8), 65 (6), 58 (100), 41 (6%).
4.3.37. (R)-Dipropyl 1-benzyloxycarbonylaminopro-
panephosphonate (9f). Colourless oil; [Found: C, 57.07;
H, 7.80; N, 3.67. C17H28NO5P requires C, 57.13; H, 7.90; N,
3.92]; [a]2D0¼222.9 (c 0.80, CH3OH); nmax (liquid film)
3237, 2970, 2938, 2880, 1721, 1540, 1456, 1282, 1230,
1064, 990 cm21; dH(300 MHz, CDCl3) 7.37–7.28 (5H, m,
C6H5), 5.18–5.02 (3H, m, NH, OCH2Ph), 4.04–3.94 (5H,
m, OCH2CH3, CHNH), 1.98–1.83 (1H, m, CHCH2CH3),
1.71–1.60 (6H, m, OCH2CH2CH3, CHCH2CH3), 1.05–
0.88 (9H, m, OCH2CH2CH3, CHCH2CH3); m/z (EI) 357 (8,
Mþ), 256 (7), 222 (8), 192 (17), 166 (4), 148 (46), 123 (5),
91 (100), 83 (7), 65 (6%).
4.3.32. (S)-Diethyl 1-acetylaminopropanephosphonate
(8d). Colourless oil; [a]2D0¼þ14.4 (c 0.50, CH3OH); nmax
(liquid film) 3437, 3265, 2980, 2936, 2879, 1661, 1549,
1234, 1052, 1025, 971 cm21; dH(300 MHz, CDCl3) 6.22
(1H, d, J¼9.9 Hz, NH), 4.43–4.43 (1H, m, CHNH), 4.18–
4.05 (4H, m, OCH2CH3), 2.05 (3H, s, COCH3), 1.98–1.81
(1H, m, CHCH2CH3), 1.67–1.50 (1H, m, CHCH2CH3),
1.35–1.25 (6H, m, OCH2CH3), 0.99 (3H, t, J¼7.2 Hz,
CHCH2CH3); m/z (EI) 237 (1, Mþ), 194 (2), 166 (3), 138
(8), 111 (10), 100 (45), 83 (9), 58 (100), 43 (16%); HRMS
(EI): Mþ, found: 237.1126. C8H20NO3P requires 237.1130.
4.3.38. (S)-Dipropyl 1-(1-methoxy)acetylaminopropane-
phosphonate (10f). Colourless oil; [a]2D0¼þ32.2 (c 1.30,
CH3OH); nmax (liquid film) 3416, 3268, 2971, 2939, 2881,
1687, 1521, 1239, 1065, 1001 cm21; dH(300 MHz, CDCl3)
6.62 (1H, d, J¼9.9 Hz, NH), 4.45–4.32 (1H, m, CHNH),
4.3.33. (S)-Diethyl 1-benzyloxycarbonylaminopropane-
phosphonate (9d). Colourless oil; [Found: C, 54.64; H,