ACCEPTED MANUSCRIPT
3.5.1.2. Diethyl
N-[2-(N-benzyloxycarbamoyl)ethyl]-N-(3-chlorobenzyl)phosphoramidate
19c as a yellow oil (0.60 g, 83%) [HRMS: m/z calculated for C21H2935ClN2O5P (MH+)
455.1503. Found 455.1498]; νmax/cm-1 1658 (C=O) and 1214 (P=O); δH/ppm (300 MHz;
CDCl3) 1.31 (6H, t, J = 7.2 Hz, 2 × CH3), 2.32 (2H, m, CH2CO), 3.24 (2H, m, NCH2CH2),
4.02-4.13 (6H, m, 2 × OCH2CH3 and NCH2Ar), 4.87 (2H, s, OCH2Ph), 7.18-7.37 (9H,
overlapping m, Ar-H) and 9.10 (1H, br s, NH); δC/ppm (75 MHz; CDCl3) 16.2 (d, JP-C = 7.2
Hz, 2 × CH3), 33.2 (CH2CO), 44.7 (NCH2CH2), 49.6 (NCH2Ar), 62.5 and 62.8 (2 ×d, 2 ×
OCH2CH3), 78.0 (OCH2Ph), 125.5, 126.5, 127.5, 127.7, 128.3, 129.1, 129.8, 134.4, 135.6 and
139.8 (Ar-C) and 168.7 (C=O).
3.5.1.3. Diethyl
N-[2-(N-benzyloxycarbamoyl)ethyl]-N-(3,4-difluorobenzyl)phosphorami-
date 19d as a yellow oil (0.53 g, 70%) [HRMS: m/z calculated for C21H28F2N2O5P (MH+)
457.1704. Found 457.1702]; νmax/cm-1 1672 (C=O) and 1233 (P=O); δH/ppm (600 MHz;
CDCl3) 1.27 (6H, t, J = 7.3 Hz, 2 × CH3), 2.28 (2H, m, CH2CO), 3.18 (2H, m, NCH2CH2),
3.96-4.08 (6H, m, 2 × OCH2CH3 and NCH2Ar), 4.87 (2H, s, OCH2Ph) and 7.02-7.36 (8H,
series of m, Ar-H); δC/ppm (150 MHz; CDCl3) 16.2 (d, JP-C = 7.0 Hz, 2 × CH3), 33.4
(CH2CO), 44.4 (NCH2CH2), 49.4 (NCH2Ar), 62.6 (d, JP-C = 5.4 Hz, 2 × OCH2CH3), 78.1
(OCH2Ph), 116.4 (d, JF-C = 17.5 Hz), 117.3 (m), 123.2 (m), 128.6, 128.7, 129.1, 135.6, 137.0
(d, JF–C = 211.5 Hz), 149.4 (dd, JF–C = 13.6 and 244.5 Hz) and 150.9 (ddd, JF–C = 6.8, 9.1 and
247.5 Hz) (Ar-C) and 168.9 (C=O).
3.5.1.4. Diethyl
N-[2-(N-benzyloxycarbamoyl)ethyl]-N-(3-fluorobenzyl)phosphoramidate
19e as a yellow oil (0.37 g, 72%) [HRMS: m/z calculated for C21H29FN2O5P (MH+) 439.1798.
Found 439.1791]; νmax/cm-1 1674 (C=O) and 1231 (P=O); δH/ppm (600 MHz; CDCl3) 1.33
(6H, t, J = 7.3 Hz, 2 × CH3), 2.33 (2H, m, CH2CO), 3.26 (2H, m, NCH2CH2), 4.03-4.16 (6H,
m, 2 × OCH2CH3 and NCH2Ar), 4.92 (2H, s, OCH2Ph), 6.98 (1H, br s, NH), 7.07-7.41 (9H,
series of m, Ar-H) and 7.29-7.41 (4H, overlapping m, Ar-H); δC/ppm (150 MHz; CDCl3) 16.3
(d, JP-C = 7.0 Hz, 2 × CH3), 33.6 (CH2CO), 45.0 (NCH2CH2), 49.9 (NCH2Ar), 62.7 (d, JP-C
5.4 Hz, 2 × OCH2CH3), 78.2 (OCH2Ph), 114.4 (dd, JF–C = 8.7 and 20.7 Hz), 115.1 (d, JF–C
=
=
21.6 Hz), 122.9 (d, JF–C = 2.4 Hz), 124.0, 128.7 (m), 129.2, 130.2 (d, JF–C = 8.0 Hz), 135.6,
142.5 and 163.1 (d, JF–C = 246.5 Hz) (Ar-C) and 169.0 (C=O).
3.5.1.5. Diethyl N-[2-(N-benzyloxycarbamoyl)ethyl]-N-furfurylphosphoramidate 19f as a
yellow oil (0.47 g, 70%) [HRMS: m/z calculated for C19H28N2O6P (MH+) 411.1685. Found
411.1674]; νmax/cm-1 1667 (C=O) and 1226 (P=O); δH/ppm (600 MHz; CDCl3) 1.27 (6H, t, J =
7.1 Hz, 2 × CH3), 2.27 (2H, m, CH2CO), 3.28 (2H, m, NCH2CH2), 3.95-4.02 (4H, 2 × m, 2 ×
OCH2CH3), 4.08 (2H, d, JP-H = 9.5 Hz, NCH2Ar), 4.88 (2H, s, OCH2Ph), 6.26 (1H, d, J = 2.3
Hz, Ar-H), 6.29 (1H, t, J = 2.4 Hz, Ar-H), 7.33-7.39 (6H, overlapping m, Ar-H) and 9.66 (1H,
br d, NH); δC/ppm (150 MHz; CDCl3) 16.2 (d, JP-C = 7.3 Hz, 2 × CH3), 33.7 (CH2CO), 42.8
(NCH2CH2), 43.2 (NCH2Ar), 62.7 (d, JP-C = 5.5 Hz, 2 × OCH2CH3), 78.1 (OCH2Ph), 109.1,
110.5, 127.6, 128.7, 129.2, 135.7, 142.5 and 151.1 (Ar-C) and 168.9 (C=O).
3.5.1.6. Diethyl N-[2-(N-benzyloxycarbamoyl)ethyl]-N-(3-nitrobenzyl)phosphoramidate 19g
as a yellow oil (1.9 g, 78%) [HRMS: m/z calculated for C21H29N3O7P (MH+) 466.1743. Found
466.1754]; νmax/cm-1 1668 (C=O) and 1229 (P=O); δH/ppm (600 MHz; CDCl3) 1.30 (6H, t, J =
7.3 Hz, 2 × CH3), 2.33 (2H, m, CH2CO), 3.21 (2H, m, NCH2CH2), 4.01-4.04 (4H, m, 2 ×
OCH2CH3), 4.25 (2H, d, JP-H = 10.2 Hz, NCH2Ar), 4.87 (2H, s, OCH2Ph), 7.31-7.36 (5H,
overlapping m, Ar-H), 7.49 (1H, m, Ar-H), 7.66 (1H, m, Ar-H), 8.11 (1H, m, Ar-H). 8.24 (1H,
m, Ar-H) and 10.0 (1H, s, NH); δC/ppm (150 MHz; CDCl3) 16.2 (d, JP-C = 7.0 Hz, 2 × CH3),
33.3 (CH2CO), 42.4 (NCH2CH2), 49.5 (NCH2Ar), 63.1 (d, JP-C = 5.7 Hz, 2 × OCH2CH3), 78.0
(OCH2Ph), 122.2, 122.6, 123.0, 128.5, 129.0, 129.6, 134.4, 135.5, 140.1 and 148.4 (Ar-C) and
168.7 (C=O).
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