Dibenzyl 2-(Tetrahydro-2H-Pyran-2-Yloxy)Ethyl Phosphate (2A)

Dibenzyl 2-(tetrahydro-2H-pyran-2-yloxy)ethyl phosphate (2a)

Yield: 75%. 1H-NMR (CDCl3): 1.46–1.83 (6H, m), 3.43–3.64 (2H, m), 3.79–3.89 (2H, m), 4.13–4.20 (2H, m), 4.61 (1H, t, J=3.6 Hz), 5.06 (4H, d, J=7.5 Hz), 7.32–7.39 (10H, m). FAB-MS m/z: 429.2 (M+Na)+.

Dibenzyl 3-(tetrahydro-2H-pyran-2-yloxy)propyl phosphate (2b)

Yield: 93%. 1H-NMR (CDCl3) : 1.25–1.92 (8H, m), 3.38–3.48 (2H, m), 3.75–3.83 (2H, m), 4.09–4.17 (2H, m), 4.53 (1H, t, J=3.9 Hz), 5.04 (4H, dd, J=2.1, 10.2 Hz), 7.31–7.35 (10H, m).FAB-MS m/z: .443.3 (M+Na)+.

Dibenzyl 4-(tetrahydro-2H-pyran-2-yloxy)butyl phosphate (2c)

Yield: 60%. 1H-NMR (CDCl3) : 1.25–1.75 (10H, m), 3.32–3.51 (2H, m), 3.68–3.86 (2H, m), 4.04 (2H, quart, J=6.6 Hz), 4.54 (1H, t, J=4.2 Hz), 5.03 (4H, dd, J=2.1, 10.5 Hz), 7.30–7.36 (10H, m). FAB-MS m/z: .457.3 (M+Na)+.

Dibenzyl 6-(tetrahydro-2H-pyran-2-yloxy)hexyl phosphate (2d)

Yield: 92%. 1H-NMR (CDCl3) : 1.32–1.83 (14H, m), 3.32–3.51 (2H, m), 3.67–3.86 (2H, m), 3.97 (2H, quart, J=6.6 Hz), 4.56 (1H, t, J=4.2 Hz), 5.03 (4H, dd, J=2.7, 10.8 Hz), 7.30–7.37 (10H, m). FAB-MS m/z: 485.4 (M+Na)+.

Dibenzyl 12-(tetrahydro-2H-pyran-2-yloxy)dodecyl phosphate (2e)

Yield: 65%. 1H-NMR (CDCl3) : 1.24 (16H, brs), 1.31–1.91 (10H, m), 3.34–3.53 (2H, m), 3.69–3.91 (2H, m), 3.98 (2H, quart, J=6.6 Hz), 4.58 (1H, t, J=4.2 Hz), 5.03 (4H, dd, J=2.1, 11.1 Hz), 7.28–7.39 (10H, m).FAB-MS m/z: 569.4 (M+Na)+.

Dibenzyl 2-hydroxyethyl phosphate (3a)

Yield: 70%. 1H-NMR (CDCl3) : 3.04 (1H, brs), 3.73 (2H, t, J=4.2 Hz), 4.05–4.11 (2H, m), 5.06 (4H, dd, J=3.3, 11.7 Hz), 7.29–7.39 (10H, m). FAB-MS m/z: 323.1 (M+H)+.

Dibenzyl 3-hydroxypropyl phosphate (3b)

Yield: 70%. 1H-NMR (CDCl3) : 1.76–1.84 (2H, m), 3.66 (2H, t, J=6.0 Hz), 4.10–4.16 (2H, m), 5.02 (4H, dd, J=2.1, 10.5 Hz), 7.28–7.37 (10H, m). FAB-MS m/z: 337.2 (M+H)+.

Dibenzyl 4-butyl phosphate (3c)

Yield: 66%. 1H-NMR (CDCl3) : 1.18–1.74 (4H, m), 3.18 (1H, brs), 3.57 (2H, t, J=6.3 Hz), 4.00 (2H, quart, J=6.6 Hz), 5.01 (4H, dd, J=1.8, 10.2 Hz), 7.27–7.36 (10H, m).FAB-MS m/z: 351.2 (M+H)+.

Dibenzyl 6-hexyl phosphate (3d)

Yield: 44%. 1H-NMR (CDCl3) : 1.27–1.63 (8H, m), 1.85 (1H, brs), 3.60 (2H, t, J=6.3 Hz), 3.99 (2H, quart, J=6.6 Hz), 5.03 (4H, dd, J=2.7, 10.5 Hz), 7.28–7.39 (10H, m).FAB-MS m/z: 379.1 (M+H)+.

Dibenzyl 12-hydroxydodecyl phosphate (3e)

Yield: 87%. 1H-NMR (CDCl3) : 1.25 (14H, brs), 1,31–1.60 (6H, m), 3.64 (2H, t, J=6.6 Hz), 3.98 (2H, quart, J=6.6 Hz), 5.03 (4H, dd, J=2.1, 10.2 Hz), 7.31–7.40 (10H, m). FAB-MS m/z: 463.3 (M+H)+.

2-{[Bis(benzyloxy)phosphoryl]oxy}ethyl (11ß,13E,15S)-9-oxo-11,15-bis(tetrahydro-2H-pyran-2-yloxy)prost-13-en-1-oate (5a)

Yield: 81%. 1H-NMR (CDCl3) : 0.88 (3H, t, J=6.6 Hz), 1.23–2.81 (36H, m), 3.46-3.51 (2H, m), 3.83–4.11 (8H, m), 4.64–4.73 (2H, m), 5.03 (4H, dd, J=1.5, 10.2 Hz), 5.38–5.69 (2H, m), 7.30–7.39 (10H, m). FAB-MS m/z: 849.5 (M+Na)+.

3-{[Bis(benzyloxy)phosphoryl]oxy}propyl (11ß,13E,15S)-9-oxo-11,15-bis(tetrahydro-2H-pyran-2-yloxy)prost-13-en-1-oate (5b)

Yield: 63%. 1H-NMR (CDCl3) : 0.88 (3H, t, J=6.3 Hz), 1.26–2.82 (38H, m), 3.46–3.50 (2H, m), 3.84–4.12 (8H, m), 4.64–4.74 (2H, m), 5.04 (4H, dd, J=2.4, 10.8 Hz), 5.38–5.63 (2H, m), 7.32–7.38 (10H, m). FAB-MS m/z: 863.6 (M+Na)+.

4-{[Bis(benzyloxy)phosphoryl]oxy}butyl (11ß,13E,15S)-9-oxo-11,15-bis(tetrahydro-2H-pyran-2-yloxy)prost-13-en-1-oate (5c)

Yield: 75%. 1H-NMR (CDCl3) : 0.81 (3H, t, J=6.6 Hz), 1.18–2.73 (40H, m), 3.39–3.42 (2H, m), 3.76–4.02 (8H, m), 4.57–4.66 (2H, m), 4.96 (4H, dd, J=3.0, 11.4 Hz), 5.30–5.62 (2H, m), 7.23–7.31 (10H, m). FAB-MS m/z: 877.6 (M+Na)+.

6-{[Bis(benzyloxy)phosphoryl]oxy}hexyl (11ß,13E,15S)-9-oxo-11,15-bis(tetrahydro-2H-pyran-2-yloxy)prost-13-en-1-oate (5d)

Yield: 62%. 1H-NMR (CDCl3): 0.88 (3H, t, J=6.6 Hz), 1.28–2.81 (44H, m), 3.46–3.50 (2H, m), 3.84–4.04 (8H, m), 4.63–4.73 (2H, m), 5.03 (4H, dd, J=2.7, 11.1 Hz), 5.38–5.69 (2H, m), 7.29–7.36 (10H, m). FAB-MS m/z: 905.5 (M+Na)+.

12-{[Bis(benzyloxy)phosphoryl]oxy}dodecyl (11ß,13E,15S)-9-oxo-11,15-bis(tetrahydro-2H-pyran-2-yloxy)prost-13-en-1-oate (5e)

Yield: 76%. 1H-NMR (CDCl3): 0.88 (3H, t, J=7.2 Hz), 1.28–2.81 (56H, m), 3.46–3.50 (2H, m), 3.84–4.11 (8H, m), 4.63–4.73 (2H, m), 5.06 (4H, dd, J=2.1, 14.1 Hz), 5.38–5.70 (2H, m), 7.31–7.36 (10H, m).FAB-MS m/z: 989.7 (M+Na)+.

2-{[Bis(benzyloxy)phosphoryl]oxy}ethyl(11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate (6a)

Yield: 65%. 1H-NMR (CD3OD) : 0.88 (3H, t, J=6.9 Hz), 1.23–1.55 (18H, m), 1.99–2.35 (5H, m), 2.61–2.70 (1H, m), 3.99–4.23 (6H, m), 5.05 (4H, d, J=8.7 Hz), 5.57–5.60 (2H, m), 7.28–7.38 (10H, m). FAB-MS m/z: 681.4 (M+Na)+.

3-{[Bis(benzyloxy)phosphoryl]oxy}propyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate (6b)

Yield: 63%. 1H-NMR (CD3OD) : 0.79 (3H, t, J=7.2 Hz), 1.16–1.47 (18H, m), 1.81–2.23 (7H, m), 2.52–2.61 (1H, m), 3.92–4.02 (6H, m), 4.94 (4H, dd, J=0.9, 9.6 Hz), 5.48–5.51 (2H, m), 7.23–7.28 (10H, m).FAB-MS m/z: 695.3 (M+Na)+.

4-{[Bis(benzyloxy)phosphoryl]oxy}butyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate (6c)

Yield: 56%. 1H-NMR (CD3OD) : 0.89 (3H, t, J=6.9 Hz), 1.27–1.65 (22H, m), 2.02–2.35 (5H, m), 2.61–2.70 (1H, m), 3.97–4.07 (6H, m), 5.03 (4H, dd, J=1.5, 10.5 Hz), 5.58–5.60 (2H, m), 7.31–7.39 (10H, m). FAB-MS m/z: 709.5 (M+Na)+.

6-{[Bis(benzyloxy)phosphoryl]oxy}hexyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate (6d)

Yield: 39%. 1H-NMR (CD3OD) : 0.80 (3H, t, J=7.2 Hz), 1.19–1.49 (26H, m), 1.93–2.27 (5H, m), 2.52–2.61 (1H, m), 3.82–3.98 (6H, m), 4.86 (4H, dd, J=1.2, 10.2 Hz), 5.49–5.51 (2H, m), 7.23–7.28 (10H, m). FAB-MS m/z: 737.4 (M+Na)+.

12-{[Bis(benzyloxy)phosphoryl]oxy}dodecyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate (6e)

Yield: 48%. 1H-NMR (CD3OD) : 0.90 (3H, t, J=6.9 Hz), 1.27–1.60 (38H, m), 2.25–2.36 (5H, m), 2.62–2.70 (1H, m), 3.74–4.07 (6H, m), 5.03 (4H, dd, J=1.2, 10.2 Hz), 5.58–5.61 (2H, m), 7.32–7.37 (10H, m).FAB-MS m/z: 821.5 (M+Na)+.

2-(Phosphonooxy)ethyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate sodium salt (7a)

Yield: 100%. 1H-NMR (CD3OD) : 0.83 (3H, t, J=6.6 Hz), 1.15–1.52 (18H, m), 1.96–2.29 (5H, m), 2.54–2.62 (1H, m), 3.91–3.97 (4H, m), 4.14 (2H, t, J=5.4 Hz), 5.50–5.53 (2H, m).FAB-MS m/z: 523.2 (M+H)+; HR-FAB-MS m/z: (M+H)+calcd for C22H38O9PNa2, 523.2049; found, 523.2053.

3-(phosphonooxy)propyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate sodium salt (7b)

Yield: 100%. 1H-NMR (CD3OD) : 0.81 (3H, t, J=6.9 Hz), 1.22–1.44 (18H, m), 1.84–2.26 (7H, m), 2.54–2.62 (1H, m), 3.81–3.98 (4H, m), 4.09 (2H, t, J=6.6 Hz), 5.50–5.52 (2H, m). FAB-MS m/z: 537.1 (M+H)+; HR-FAB-MS m/z: (M+H)+calcd for C23H40O9PNa2, 537.2205; found, 523.2245.

4-(Phosphonooxy)butyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate sodium salt (7c)

Yield: 89%. 1H-NMR (CD3OD) : 0.81 (3H, t, J=6.9 Hz), 1.14–1.68 (22H, m), 1.92–2.24 (5H, m), 2.53–2.62 (1H, m), 3.78 (2H, quart, J=5.7 Hz). 3.90–4.03 (4H, m), 5.50–5.52 (2H, m).FAB-MS m/z: 551.2 (M+H)+; HR-FAB-MS m/z: (M+H)+calcd for C24H42O9PNa2, 551.2362; found, 551.2374.

6-(Phosphonooxy)hexyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate sodium salt (7d)

Yield: 98%. 1H-NMR (CD3OD) : 0.81 (3H, t, J=6.9 Hz), 1.15–1.59 (26H, m), 1.94–2.31 (5H, m), 2.54–2.62 (1H, m), 3.76 (2H, quart, J=6.3 Hz), 3.92–3.99 (4H, m), 5.50–5.52 (2H, m). FAB-MS m/z: 579.3 (M+H)+; HR-FAB-MS m/z: (M+H)+calcd for C26H46O9PNa2, 579.2675; found, 579.2709.

12-(Phosphonooxy)dodecyl (11ß,13E,15S)-11,15-dihydroxy-9-oxoprost-13-en-1-oate sodium salt (7e)

Yield: 100%. 1H-NMR (CD3OD) : 0.81 (3H, t, J=6.9 Hz), 1.14–1.52 (38H, m), 1.84–2.35 (5H, m), 2.54–2.62 (1H, m), 3.75 (2H, quart, J=6.3 Hz), 3.92–4.00 (4H, m), 5.50–5.52 (2H, m).FAB-MS m/z: 663.4 (M+H)+; HR-FAB-MS m/z: (M+H)+calcd for C32H58O9PNa2, 663.3614; found, 663.3623.

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