Sphingosine-1-phosphate Analogues
2747
(75 MHz, CDCl3) d 156.5, 155.1, 141.3, 133.9, 129.8, 128.6, 128.3, 125.9,
114.4, 79.8, 65.8 (d, J ¼ 6.0 Hz), 65.6, 54.3 (d, J ¼ 6.0 Hz), 40.9, 28.2; 31P
NMR (300 MHz, CDCl3) d 21.70; IR (film) 2957, 2534, 1714, 1608, 1510,
1270, 1240, 1172, 1041, 849 cm21; ESI-MS: m/z ¼ 485 [Mþ þ 23], 953
[2Mþ þ 23]; [a]D ¼ 231.9 (c, 0.5, CHCl3, 208C).
(R)-tert-Butyl-N-[3-(4-chloro-3-methylphenoxy)-1-
(dimethoxyphosphoryloxy)propan-2-yl]carbamate (11c)
Yield: 76%; TLC Rf ¼ 0.33 (1:1 n-Hex/EtOAc); 1H NMR (300 MHz, CDCl3)
d 7.20 (d, J ¼ 8.7 Hz, 1H), 6.77 (d, J ¼ 2.9 Hz, 1H), 6.67 (dd, J ¼ 8.6 Hz,
2.9 Hz, 1H), 5.14 (d broad, 1H), 4.17 (m, 3H), 4.07 (m, 1H), 3.93 (dd,
J ¼ 9.3 Hz, 5.85 Hz, 1H), 3.75 (d, J ¼ 11.1 Hz, 3H), 3.70 (d, J ¼ 11.1 Hz,
3H), 2.31 (s, 3H), 1.44 (s, 9H); 13C NMR (75 MHz, CDCl3) d 156.6, 155.1,
137.0, 129.5, 126.3, 116.9, 113.0, 79.9, 65.7, 65.6, 54.0 (d, J ¼ 6.04 Hz),
28.2, 20.1; 31P NMR (300 MHz, CDCl3) d 21.76; IR (film) 2984, 1710,
1530, 1479, 1276, 1245, 1163, 1041, 849 cm21; ESI-MS: m/z ¼ 446
[Mþ þ 23], 869 [2Mþ þ 23]; [a]D ¼ 221.9 (c, 1.0, CHCl3, 208C).
(R)-tert-Butyl-N-[1-(dimethoxyphosphoryloxy)-3-(4-propylphenoxy)
propan-2-yl]carbamate (11d)
Yield: 83%; TLC Rf ¼ 0.35 (1:1 n-Hex/EtOAc); 1H NMR (300 MHz, CDCl3)
d 7.07 (d, J ¼ 8.7 Hz, 2H), 6.81 (d, J ¼ 8.7 Hz, 2H), 5.15 (d broad, 1H), 4.18
(m, 3H), 4.09 (m, 1H), 3.96 (dd, J ¼ 9.3 Hz, 5.4 Hz, 1H), 3.74 (d, J ¼ 11.1 Hz,
3H), 3.70 (d, J ¼ 11.1 Hz, 3H), 2.51 (t, J ¼ 7.3 Hz, 2H), 1.59 (sx, J ¼ 7.3 Hz,
2H), 1.44 (s, 9H), 0.90 (t, J ¼ 7.3 Hz, 3H); 13C NMR (75 MHz, CDCl3) d
156.2, 155.0, 135.7, 128.2, 114.0, 80.0, 66.1 (d, J ¼ 6.0 Hz), 66.0, 54.1
(d, J ¼ 6.0 Hz), 37.3, 28.1, 24.0, 13.9; 31P NMR (300 MHz, CDCl3) d
21.71; IR (film) 2956, 2935, 2873, 1709, 1611, 1509, 1463, 1276, 1239,
1175, 1042, 845 cm21; ESI-MS: m/z ¼ 440 [Mþ þ 23], 857 [2Mþ þ 23];
[a]D ¼ 223.2 (c, 1.0, CHCl3, 208C).
(R)-tert-Butyl-N-[3-(4-decyloxyphenoxy)-3-(dimethoxyphosphoryloxy)
propan-2-yl]carbamate (11e)
Yield: 82%; TLC Rf ¼ 0.37 (1:1 n-Hex/EtOAc); 1H NMR (500 MHz, CDCl3)
d 6.82 (m, 4H), 5.18 (d broad, 1H), 4.27 (m, 1H), 4.17 (m,2H), 4.06 (m, 1H),
3.95 (m, 1H), 3.89 (t, J ¼ 6.3 Hz, 2H), 3.76 (d, J ¼ 11.1 Hz, 3H), 3.72
(d, J ¼ 11.1 Hz, 3H), 1.75 (q, J ¼ 7.3 Hz, 2H), 1.45 (s, 9H), 1.27 (m, 14H),
0.88 (t, J ¼ 6.8 Hz, 3H); 13C NMR (125 MHz, CDCl3) d 155.5, 153.9,
152.4, 115.5, 80.0, 68.9, 66.6, 54.7 (d, J ¼ 5.4 Hz), 32.1, 29.8, 29.7, 29.6,
29.5, 29.4, 28.5, 26.2, 22.9, 21.2, 14.3; IR (film) cm21 2929, 2854, 1713,
1526, 1272, 1171, 1037, 850 cm21; ESI-MS: m/z ¼ 432 [Mþ-Boc], 554
[Mþ þ 23], 1085 [2Mþ þ 23]; [a]D ¼ 22.6 (c, 1.0, CHCl3, 208C).