Table IIb.
13C and31P NMR data of compounds 5, 6, 16 and 22–27x
| Compound | Solvent | C-1‘ | C-2‘ | C-3‘ | C-4‘ | Base | 31P | 19F |
|---|---|---|---|---|---|---|---|---|
 |
D2O a | 88.14 1,F = 34.0 |
96.60 2,F = 192.0 |
75.51 3,F = 15.1 |
112.10 4,P = 12.1 4,F = 3.2 |
C-2: 155.51 C-4: 151.41 C-5: 121.14 C-6: 158.18 C-8: 142.68 |
14.93 | −210.06 |
 |
D2O b | 87.78 | 96.18 | 75.27 | 111.87 | C-2: n.d. C-4: 154.37 C-5: 118.81 C-6: n.d. C-8: 140.52 |
14.15 | −209.59 |
 |
DMSO c | 86.31 1,F = 34.4 |
91.24 2,F = 193.1 |
74.45 3,F = 14.0 |
106.69 4,P = 12.4 4,F = 1.1 |
C-2: 152.62 C-4: 152.14 C-5: 125.77 C-6: 150.94 C-8: 143.32 |
18.29 | −204.85 |
 |
DMSO d | 86.57 1,F = 15.0 |
91.14 2,F = 192.6 |
74.33 3,F = 13.9 |
106.95 4,P = 13.2 |
C-2: 150.19 C-4: 154.35 C-5: 120.32 C-6: 152.57 C-8: 144.37 |
18.93 | −203.23 |
 |
DMSO e | 82.10 1,F = 15.6 |
88.90 2,F = 197.1 |
74.78 3,F = 14.0 |
105.04 4,P = 11.7 |
C-2: 152.33 C-4: 152.13 C-5: 124.96 C-6: 150.75 C-8: 142.98 8,F = 5.5 |
19.18 | −207.71 |
 |
DMSO f | 82.59 1,F = 15.7 |
88.63 2,F = 197.5 |
74.61 3,F = 16.1 |
105.42 4,P = 12.2 |
C-2: 150.19 C-4: 154.55 C-5: 119.67 C-6: 152.75 C-8: 144.05 8,F = 5.1 |
19.09 | −206.65 |
 |
D2O g | 89.27 | 77.15 | 76.56 | 111.95 4,P = 11.8 |
C-2: 156.79 C-4: 154.74 C-5: 118.76 C-6: 161.68 C-8: 140.52 |
14.35 | – |
 |
D2O h | 91.41 | 75.65 | 76.69 | 112.28 4,P = 11.0 |
C-2: 159.86 C-4: 152.00 C-5: 127.19 C-6: 158.94 |
15.93 | – |
 |
D2O i | 91.09 | 76.23 | 76.57 | 112.17 4,P = 10.9 |
C-2: 158.82 C-4: 155.02 C-5: 127.40 C-6: 160.97 |
15.38 | – |
 |
DMSO j | 85.82 | 74.08 | 74.44 | 106.20 4,P = 12.4 |
C-2: 152.16 C-4: 152.38 C-5: 125.72 C-6: 150.80 C-8: 149.09 |
19.16 | – |
 |
DMSO k | 86.12 | 73.82 | 74.43 | 106.34 4,P = 13.4 |
C-2: 150.23 C-4: 154.72 C-5: 120.36 C-6: 152.70 C-8: 144.24 |
19.42 | – |
 |
DMSO l | 88.35 | 72.46 | 73.92 | 108.70 4,P = 11.8 |
C-2: 157.39 C-4: 149.95 C-5: 124.14 C-6: 156.38 |
19.77 | – |
 |
DMSOm | 86.13 | 73.22 | 74.63 | 106.54 4,P = 12.9 |
C-2: 155.69 C-4: 152.30 C-5: 124.66 C-6: 156.25 |
19.06 | – |
 |
DMSO n | 89.10 | 73.65 | 74.75 | 107.15 4,P = 12.4 |
C-2: 154.29 C-4: 153.72 C-5: 113.66 C-6: 161.55 |
18.70 | – |
 |
DMSO o | 86.94 | 73.36 | 74.41 | 106.97 4,P = 12.5 |
C-2: 157.61 C-4: 149.56 C-5: 124.12 C-6: 156.46 |
18.20 | – |
 |
DMSO p | 91.99 | 70.82 | 72.63 | 107.40 4,P = 11.7 |
C-2: 157.80 C-4: 157.12 C-5: 126.12 C-6: 158.00 |
n.d. | – |
 |
D2O q | 88.24 1,F = 34.1 |
96.51 2,F = 192.3 |
75.42 3,F = 14.9 |
112.14 4,P = 12.2 4,F = 3.2 |
C-2: 155.49 C-4: 151.68 C-5: 121.36 C-6: 158.30 C-8: 142.89 |
Pα: 8.39 α,β = 25.6 Pβ: 22.10 β,α = 25.6 β,γ = 19.7 Pγ: 9.48 γ,β = 19.7 |
−210.72 |
 |
D2O r | 87.85 1,F = 33.9 |
95.38 2,F = 191.8 |
75.11 3,F = 14.9 |
111.72 4,P = 12.0 4,F = 3.2 |
C-2: 156.71 C-4: 154.34 C-5: 118.85 C-6: 161.67 C-8: 140.50 |
Pα: 8.62 α,β = 25.7 Pβ: 22.02 β,α = 25.7 β,γ = 16.7 Pγ: 9.60 γ,β = 16.7 |
−210.89 |
 |
D2O s | 89.36 | 76.78 | 76.41 | 111.82 4,P = 12.0 |
C-2: 156.79 C-4: 154.81 C-5: 118.84 C-6: 161.75 C-8: 140.59 |
Pα: 8.36 α,β = 25.8 Pβ: 22.51 β,α = 25.8 β,γ = 19.6 Pγ: 9.82 γ,β = 19.6 |
– |
 |
D2O t | 91.38 | 75.54 | 76.52 | 112.34 4,P = 9.8 |
C-2: 159.95 C-4: 152.13 C-5: 127.33 C-6: 159.08 |
Pα: 9.06 α,β = 26.2 Pβ: 22.03 β,α = 26.2 β,γ = 19.4 Pγ: 9.27 γ,β = 19.4 |
– |
 |
D2O u | 91.34 | 74.71 | 76.23 | 111.88 4,P = 10.5 |
C-2: 160.82 C-4: 154.82 C-5: 127.39 C-6: 158.54 |
Pα: 9.21 α,β = 26.2 Pβ: 22.30 β,α = 26.2 β,γ = 19.4 Pγ: 9.84 γ,β = 19.4 |
– |
 Mixture of diastereomers 53:47 |
DMSO v Major |
84.73 1,F = 33.0 |
93.16 2,F = 191.1 |
72.35 3,F = 15.0 |
108.30 4,P = 10.8 4,F = 4.1 |
C-2: 153.24 C-4: 149.67 C-5: 118.93 C-6: 156.33 C-8: 139.06 |
23.18 | −211.17 |
| Minor | 84.63 1,F = 33.2 |
93.30 2,F = 191.2 |
72.30 3,F = 15.0 |
108.38 4,P = 11.8 4,F = 3.2 |
C-2: 153.24 C-4: 149.68 C-5: 118.88 C-6: 156.33 C-8: 139.03 |
22.74 | −211.28 | |
 Mixture of diastereomers 57:43 |
DMSOw Major |
84.14 1,F = 32.5 |
93.37 2,F = 191.7 |
72.22 3,F = 15.0 |
108.00 4,P = 4.2 |
C-2: 154.22 C-4: 151.52 C-5: 116.69 C-6: 156.85 C-8: 135.00 |
23.29 | −212.34 |
| minor | 84.11 1,F = 32.5 |
93.20 2,F = 191.6 |
72.16 3,F = 15.0 |
108.08 4,P = 4.2 |
C-2: 154.19 C-4: 151.48 C-5: 116.78 C-6: 156.88 C-8: 135.23 |
22.95 | −212.81 |
Substituents.
O–CH2–P = O(OH)2: 68.13 d, J = 155.9 Hz.
O–CH2–P = O(OH)2: 68.59.
O–CH2–P = O(OiPr)2: 62.62 d, J = 166.0 Hz (P–CH2–O), 71.02 d, J = 6.3 Hz (2x O–CH<), 23.97 d, J = 3.5 Hz, 23.99 d, J = 3.5 Hz, 24.04 d, J = 4.4 Hz, 24.12 d, J = 3.8 Hz (2x OiPr); 3-OBz: 164.78 (C O), 128.50 (i-ArC), 129.86 (2x o-ArC), 129.32 (2x m-ArC), 134.52 (p-ArC); NHBz: 165.98 (C O), 133.55 (i-ArC), 128.78 (2x o-ArC and 2x m-ArC), 132.82 (p-ArC).
NHAc: 168.71 (C O), 24.71 (CH3); 3-OBz: 164.45 (C O), 128.53 (i-ArC), 129.70 (2x o-ArC), 129.22 (2x m-ArC), 134.35 (p-ArC); O–CH2–P = O(OiPr)2: 62.24 d, J = 166.3 Hz (P–CH2–O), 70.85 d, J = 6.3 Hz (2x O–CH<), 23.69 d, J = 6.3 Hz, 23.72 d, J = 4.4 Hz, 23.86 d, J = 4.0 Hz, 23.89 d, J = 4.0 Hz (2x OiPr); O–CO–N(C6H5)2: 155.54 (C O), 141.75 (2x i-ArC), 126.67 (4x o-ArC), 129.61 (4x m-ArC), 127.10 (2x p-ArC).
O–CH2–P = O(OiPr)2: 62.31 d, J = 165.8 Hz (P–CH2–O), 70.80 d, J = 6.2 Hz and 70.81 d, J = 6.2 Hz (2x O–CH<), 23.84 d, J = 4.6 Hz, 23.85 d, J = 4.4 Hz and 23.98 d, 2C, J = 3.8 Hz (2x OiPr); 3-OBz: 164.64 (C O), 128.42 (i-ArC), 129.72 (2x o-ArC), 129.23 (2x m-ArC), 134.40 (p-ArC); 6-NHBz: 165.85 (C O), 133.45 (i-ArC), 128.71 (2x o-ArC), 128.68 (2x m-ArC), 132.72 (p-ArC).
O–CH2–P = O(OiPr)2: 62.47 d, J = 166.0 Hz (P–CH2–O), 70.77 d, J = 5.9 Hz (2x O–CH<), 23.79 d, J = 4.5 Hz, 23.81 d, J = 4.5 Hz and 23.95 d, 2C, J = 3.7 Hz (2x OiPr); 3-OBz: 164.62 (C O), 128.40 (i-ArC), 129.67 (2x o-ArC), 129.17 (2x m-ArC), 134.34 (p-ArC); NHAc: 169.19 (C O), 24.86 (CH3); O–CO–N(C6H5)2: 155.45 (C O), 141.71 (2x i-ArC), 127.17 (4x o-ArC), 129.60 (4x m-ArC), 127.53 (2x p-ArC).
O–CH2–P = O(OH)2: 67.95 d, J = 154.5 Hz.
O–CH2–P = O(OH)2: 66.72 d, J = 156.7 Hz.
O–CH2–P = O(OH)2: 67.37 d, J = 154.8 Hz.
O–CH2–P = O(OiPr)2: 62.09 d, J = 166.3 Hz (P–CH2–O), 70.91 d, J = 6.3 Hz and 70.92 d, J = 6.3 Hz (2x O–CH<), 23.82 d, 2C, J = 4.6 Hz, 23.94 d, J = 4.1 Hz and 23.97 d, J = 4.1 Hz (2x OiPr); 2-OBz: 164.63 (C O), 128.31 (i-ArC), 129.49 (2x o-ArC), 128.95 (2x m-ArC), 134.20 (p-ArC); 3-OBz: 164.66 (C O), 128.53 (i-ArC), 129.67 (2x o-ArC), 129.16 (2x m-ArC), 134.34 (p-ArC); NHBz: 165.82 (C O), 133.50 (i-ArC), 128.69 (2x o-ArC), 128.66 (2x m-ArC), 132.67 (p-ArC).
O–CH2–P = O(OiPr)2: 61.97 d, J = 167.1 Hz (P–CH2–O), 70.99 d, J = 6.3 Hz and 71.09 d, J = 6.3 Hz (2x O–CH<), 23.79 d, J = 4.4 Hz, 23.81 d, J = 4.4 Hz and 23.94 d, 2C, J = 3.6 Hz (2x OiPr); 2-OBz: 164.63 (C O), 128.32 (i-ArC), 129.53 (2x o-ArC), 128.93 (2x m-ArC), 134.20 (p-ArC); 3-OBz: 164.61 (C O), 128.56 (i-ArC), 129.60 (2x o-ArC), 129.18 (2x m-ArC), 134.36 (p-ArC); NHAc: 169.06 (C O), 24.76 (CH3); O–CO–N(C6H5)2: 155.53 (C O), 141.76 (2x i-ArC), 127.12 (4x o-ArC), 129.60 (4x m-ArC), 127.54 (2x p-ArC).
O–CH2–P = O(OiPr)2: 61.20 d, J = 165.2 Hz (P–CH2–O), 70.50 d, J = 6.2 Hz and 70.65 d, J = 6.2 Hz (2x O–CH<), 23.81 d, J = 4.7 Hz, 23.82 d, J = 4.5 Hz, 23.96 d, J = 3.7 Hz and 24.00 d, J = 3.7 Hz (2x OiPr).
O–CH2–P = O(OiPr)2: 61.94 d, J = 164.2 Hz (P–CH2–O), 70.87 d, J = 6.2 Hz and 70.92 d, J = 6.2 Hz (2x O–CH<), 23.75 d, J = 4.7 Hz, 23.78 d, J = 4.6 Hz, 23.93 d, J = 3.8 Hz and 23.94 d, J = 3.9 Hz (2x OiPr); 2-OBz: 164.69 (C O), 128.49 (i-ArC), 129.61 (2x o-ArC), 129.14 (2x m-ArC), 134.34 (p-ArC); 3-OBz: 164.66 (C O), 128.33 (i-ArC), 129.56 (2x o-ArC), 129.03 (2x m-ArC), 134.27 (p-ArC).
O–CH2–P = O(OiPr)2: 62.22 d, J = 165.0 Hz (P–CH2–O), 70.77 d, J = 6.2 Hz and 70.88 d, J = 6.2 Hz (2x O–CH<), 23.73 d, J = 4.5 Hz, 23.76 d, J = 4.5 Hz, 23.91 d, J = 3.5 Hz and 23.93 d, J = 3.5 Hz (2x OiPr); 2-OBz: 164.67 (C O), 128.46 (i-ArC), 129.56 (2x o-ArC), 129.13 (2x m-ArC), 134.33 (p-ArC); 3-OBz: 164.62 (C O), 128.34 (i-ArC), 129.59 (2x o-ArC), 129.02 (2x m-ArC), 134.27 (p-ArC).
O–CH2–P = O(OiPr)2: 62.13 d, J = 165.7 Hz (P–CH2–O), 70.70 d, J = 6.2 Hz and 70.83 d, J = 6.2 Hz (2x O–CH<), 23.69 d, J = 4.7 Hz, 23.74 d, J = 4.6 Hz, 23.89 d, J = 3.8 Hz and 23.92 d, J = 3.8 Hz (2x OiPr); 2-OBz: 164.67 (C O), 128.37 (i-ArC), 129.59 (2x o-ArC), 128.97 (2x m-ArC), 134.22 (p-ArC); 3-OBz: 164.72 (C O), 128.48 (i-ArC), 129.68 (2x o-ArC), 129.10 (2x m-ArC), 134.31 (p-ArC).
O–CH2–P = O(OiPr)2: 62.14 d, J = 166.0 Hz (P–CH2–O), 71.04 d, J = 6.3 Hz and 71.06 d, J = 6.3 Hz (2x O–CH<), 23.96 d, 2C, J = 4.4 Hz, 24.07 d, J = 3.6 Hz and 24.08 d, J = 3.8 Hz (2x OiPr); 2-OBz: 163.83 (C O), 127.81 (i-ArC), 129.03 (2x o-ArC), 128.74 (2x m-ArC), 134.22 (p-ArC); 3-OBz: 164.81 (C O), 128.47 (i-ArC), 129.94 (2x o-ArC), 128.99 (2x m-ArC), 134.22 (p-ArC).
O–CH2–P( = O)(OH)–O–P( = O)(OH)–O–P( = O)(OH)2: 67.24 d, J = 164.5 Hz (P–CH2–O).
O–CH2–P( = O)(OH)–O–P( = O)(OH)–O–P( = O)(OH)2: 66.96 d, J = 164.9 Hz (P–CH2–O).
O–CH2–P( = O)(OH)–O–P( = O)(OH)–O–P( = O)(OH)2: 66.54 d, J = 164.8 Hz (P–CH2–O); ’
O–CH2–P( = O)(OH)–O–P( = O)(OH)–O–P( = O)(OH)2: 66.39 d, J = 163.7 Hz (P–CH2–O).
O–CH2–P( = O)(OH)–O–P( = O)(OH)–O–P( = O)(OH)2: 66.18 d, J = 164.2 Hz (P–CH2–O).
Major diastereomer: Bu-O-CH(CH2C6H5)–CO–NH–P( = O)(O–C6H5)–CH2–O: 13.73, 18.62, 30.16, 64.49 (Bu-O-); 55.41, 39.74 (O–CH–CH2); 150.30 and 137.10 (2x i-ArC), 120.7–129.7 (10x ArC); 172.49 (C O), 63.34 d, J = 156.5 Hz (P–CH2–O); minor diastereomer: Bu-O-CH(CH2C6H5)–CO–NH–P( = O)(O–C6H5)–CH2–O: 13.68, 18.62, 30.19, 64.37 (Bu-O-); 55.35, 39.46 (O–CH–CH2); 150.25 and 137.19 (2x i-ArC), 120.7–129.7 (10x ArC); 172.71 (C O), 63.07 d, J = 154.7 Hz (P–CH2–O).
Major diastereomer: Bu-O-CH(CH2C6H5)–CO–NH–P( = O)(O–C6H5)–CH2–O: 13.66, 18.61, 30.15, 64.48 (Bu-O-); 55.37, 39.46 (O–CH–CH2); 137.06 (i-ArC), 129.41 (2x o-ArC), 128.37 (2x m-ArC), 124.56 (p-ArC) (C6H5), 172.68 d, J = 2.6 Hz (C O), 150.20 d, J = 9.2 Hz (i-ArC), 120.68 d, J = 4.5 Hz (2x o-ArC), 129.65 (2x m-ArC), 126.67 (p-ArCH) (C6H5); 62.96 d, J = 154.9 Hz (P–CH2–O); minor diastereomer: Bu-O-CH(CH2C6H5)–CO–NH–P( = O)(O–C6H5)–CH2–O: 13.70, 18.60, 30.17, 64.36 (Bu-O-); 55.33, 39.70 (O–CH–CH2); 137.18 (i-ArC), 129.52 (2x o-ArC), 128.29 (2x m-ArC), 124.62 (p-ArC) (C6H5), 172.48 d, J = 2.5 Hz (C O), 150.27 d, J = 9.2 Hz (i-ArC), 120.74 d, J = 4.5 Hz (2x o-ArC), 129.63 (2x m-ArC), 126.71 (p-ArC) (C6H5); 63.25 d, J = 157.6 Hz (P–CH2–O).
Coupling constants are written in italics in a shortened form (e.g. instead J(C1‘,F) = 34.0 Hz we type simply 1,F = 34.0).