C. Grison et al. / Carbohydrate Research 341 (2006) 1117–1129
1125
Rf (EtOAc) 0.25; IR (KBr): m 1580, 1550, 1250, 1030;
1H NMR (250 MHz, CDCl3): d 8.79 (s, 1H, H-8), 8.57
(62.9 MHz, CDCl3): d 110.5 (s), 107.7 (s, C-1), 83.7 (d,
JCP 5 Hz, C-4), 83.4 (s, C-2), 79.9 (s, C-3), 64.5 (d, JCP
5 Hz, C-5), 61.2 (d, JCP 7 Hz, OCH2CH3), 53.0 (s,
COCH3), 51.4 (d, JCP 6 Hz, POCH3), 24.7 (s, Me2C),
23.2 (s, Me2C), 22.2 (app-t, JCP 137 Hz, PCH2P), 14.6
(s, OCH2CH3), 31P NMR (101.6 MHz, CDCl3): d 19.5
(d, 1P, JPP 5 Hz), 17.3 (d, 1P, JPP 5 Hz); FABMS: m/z
419 [M+H]+, 100%.
0
0
(s, 1H, H2), 8.51 (s, 1H, H-2), 6.28 (d, 1H, J1 ;2 3 Hz,
H-10), 6.25 (d, 1H, J1 ;2 3 Hz, H-10), 5.48 (dd, 1H, J3 ;2
0
0
0
0
3 Hz, J3 ;4 6 Hz, H-30), 5.42 (dd, 1H, J3 ;2 3 Hz, J30;40
6 Hz, H-30), 5.19 (dd, 1H, H-20), 5.12 (dd, 1H, H-20),
4.60–4.52 (m, 1H, H-40), 4.45–3.95 (m, 8H, H-50,
OCH2CH3), 2.40 (app-t, 2H, JHP 21 Hz, PCH2P), 2.39
(app-t, 2H, JHP 21 Hz, PCH2P), 1.64 (s, 3H, Me2C),
1.41 (s, 3H, Me2C), 1.33 (t, 9H, J 7 Hz, OCH2CH3);
13C NMR (62.9 MHz, CDCl3): d 151.5 (s, C-8), 150.8
(s, C-5), 150.7 (s, C-5), 150.6 (s, C-4), 150.5 (s, C-4),
144.3 (s, C-2), 132.5 (s, C-6), 113.9 (s), 90.3 (s, C-10),
90.2 (s, C-10), 84.7 (d, JCP 6 Hz, C-40), 83.5 (s, C-20),
80.5 (s, C-30), 66.1 (d, JCP 5 Hz, C-50), 64.9 (d, JCP
5 Hz, C-50), 62.1 (d, JCP 6 Hz, OCH2CH3), 60.9 (d,
JCP 6 Hz, OCH2CH3), 26.4 (s, Me2C), 24.6 (app-t, JCP
137 Hz, PCH2P), 24.6 (s, Me2C), 15.7 (br s, OCH2CH3);
31P NMR (101.6 MHz, CDCl3): d 18.4 (d, 1P, JPP 5 Hz),
18.1 (d, 1P, JPP 5 Hz), 16.3 (d, 1P, JPP 5 Hz), 16.1 (d, 1P,
JPP 5 Hz); Anal. Calcd for C20H31ClN4O11P2: C, 42.23;
H, 5.49; N, 9.85; P, 10.89. Found: C, 41.95; H, 5.70; O,
9.52; P, 10.83.
0
0
0
0
4.2.9. O0-Ethyl O0-(methyl-2,3-O-isopropylidene-b-D-
ribofuranosyl)[(dimethoxythiophosphinyl)methyl]phospho-
nate 8i. From 1f (310 mg), colorless oil, 250 mg (52%).
Rf (EtOAc) 0.20; IR (KBr): m 1580, 1550, 1260, 1030,
1
830; H NMR (250 MHz, CDCl3): d 4.98 (s, 1H, H-1),
4.85 (app-t, 1H, J32 = J34 6 Hz, H-3), 4.60 (d, 1H, H-
2), 4.37–4.20 (m, 1H, H-4), 4.20–4.10 (m, 2H, H-5),
4.10–3.98 (m, 2H, OCH2CH3), 3.80 (d, 6H, JHP 14 Hz,
POCH3), 3.45 (s, 3H, COCH3), 2.79 (dd, 2H, JHP
18.5 Hz, JHP 20.5 Hz, PCH2P), 1.50 (s, 3H, Me2C),
1.37 (t, 3H, J 7 Hz, OCH2CH3), 1.33 (s, 3H, Me2C);
13C NMR (62.9 MHz, CDCl3): d 112.0 (s), 108.1 (s, C-
1), 84.6 (s, C-4), 84.4 (s, C-3), 81.2 (s, C-2), 65.6 (d,
JCP 6 Hz, C-5), 65.4 (d, JCP 6 Hz, C-5), 63.3 (d, JCP
7 Hz, OCH2CH3), 54.6 (d, JCP 6 Hz, POCH3), 53.1 (s,
COCH3), 32.9 (dd, JCP 105 Hz, JCP 133 Hz, PCH2P),
26.0 (s, Me2C), 24.5 (s, Me2C), 15.9 (d, JCP 6 Hz,
OCH2CH3), 31P NMR (101.6 MHz, CDCl3): d 58.2 (d,
1P, JPP 6 Hz), 16.2 (d, 1P, JPP 6 Hz); FABMS: m/z
435 [M+H]+, 100%.
4.2.7. O0-Methyl O0-(methyl-2,3-O-isopropylidene-b-D-
ribofuranosyl)[(diethoxyphosphinyl)methyl]phosphonate]
8g. From 1a (304 mg), colorless syrup, 250 mg (60%).
Rf (EtOAc) 0.15; IR (KBr): m 1580, 1550, 1250, 1030;
1H NMR (250 MHz, CDCl3): d 4.98 (s, 1H, H-1); 4.75
(app-t, 1H, J3,2 = J3,4 6 Hz, H-3), 4.60 (d, 1H, H-2),
4.35 (t, 1H, J3,4 6 Hz, H-4), 4.23–3.93 (m, 6H, H-5,
OCH2CH3), 3.32 (s, 3H, OCH3), 2.45 (dd, 2H, JHP
18 Hz, JHP 20 Hz, PCH2P), 1.73 (d, 3H, JHP 15 Hz,
PCH3), 1.45 (s, 3H, Me2C), 1.37 (t, 6H, J 6 Hz,
OCH2CH3), 1.33 (s, 3H, Me2C); 13C NMR (62.9 MHz,
CDCl3): d 111.4 (s); 108.5 (s, C-1), 86.8 (d, JCP 5 Hz,
C-4), 84.1 (s, C-2), 80.7 (s, C-3), 64.2 (d, JCP 6 Hz, C-
5), 63.4 (d, JCP 6 Hz, C-5), 61.7 (d, JCP 6 Hz,
OCH2CH3), 61.4 (d, JCP 6 Hz, OCH2CH3), 54.0 (s,
OCH3), 27.8 (dd, JCP 137 Hz, JCP 134 Hz, PCH2P),
25.5 (s, Me2C), 24.0 (s, Me2C), 15.9 (d, JCP 5 Hz,
OCH2CH3), 10.2 (d, JCP 82.0 Hz, PCH3); 31P NMR
(101.6 MHz, CDCl3): d 43.7 (d, 1P, JPP 5 Hz), 17,1 (d,
1P, JPP 5 Hz); FABMS: m/z 417 [M+H]+, 100%.
4.2.10. O0-Butyl O0-(methyl-2,3-O-isopropylidene-b-D-
ribofuranosyl)[(diethoxyphosphinyl)methyl]phosphonate
8l. From 1a (304 mg), colorless syrup, 299 mg (63%).
Rf (EtOAc) 0.25; IR (KBr): m 1580, 1550, 1260, 1025;
1H NMR (250 MHz, CDCl3): d 4.98 (s, 1H, H-1), 4.77
(app-t, 1H, J3,2 = J3,4 6 Hz, H-3), 4.60 (d, 1H, H-2),
4.40–4.32 (m, 1H, H-4), 4.26–4.00 (m, 8H, H-5,
OCH2CH3, OCH2CH2), 3.33 (s, 3H, OCH3), 2.49
(app-t, 2H, JHP 21 Hz, PCH2P), 1.60 (m, 2H,
CH2CH2O), 1.45 (s, 3H, Me2C), 1.41–1.31 (m, 8H,
CH2CH2CH3, OCH2CH3), 1.34 (s, 3H, Me2C), 0.95 (t,
3H, J 7 Hz, CH2CH2CH3); 13C NMR (62.9 MHz,
CDCl3): d 111.9 (s), 108.8 (s, C-1), 84.5 (s, C-2), 84.4
(br s, C-4), 81.0 (s, C-3), 65.5 (d, JCP = 6 Hz, C-5),
65.3 (d, JCP 6 Hz, C-5), 62.0 (d, JCP 6 Hz, OCH2CH3),
60.8 (d, JCP 6 Hz, OCH2CH2), 54.4 (s, OCH3), 31.9 (d,
JCP 6 Hz, CH2CH2O), 24.8 (app-t, JCP 137 Hz, PCH2P),
24.4 (s, Me2C), 18.1 (s, CH2CH2CH3), 15.8 (d, JCP 6 Hz,
OCH2CH3), 13.0 (s, CH2CH2CH3); 31P NMR
(101.6 MHz, CDCl3): d 17.6 (d, 1P, JPP 6 Hz), 16.7 (d,
1P, JPP 6 Hz); FABMS: m/z 475 [M+H]+, 100%.
4.2.8. O0-Ethyl O0-(methyl-2,3-O-isopropylidene-b-D-
ribofuranosyl)[(dimethoxyphosphinyl)methyl]phosphonate
8h. From 1e (290 mg), colorless syrup, 332 mg (68%).
Rf (EtOAc) 0.21; IR (KBr): m 1580, 1550, 1260, 1030;
1H NMR (250 MHz, CDCl3): d 4.92 (s, 1H, H-1), 4.70
(app-t, 1H, J3,2 = J3,4 6 Hz, H-3), 4.54 (d, 1H, H-2),
4.36–4.27 (m, 1H, H-4), 4.22–4.10 (m, 2H, OCH2CH3),
4.10–3.97 (m, 2H, H-5), 3.77 (d, 6H, JHP 12 Hz,
POCH3), 3.28 (s, 3H, OCH3), 2.45 (app-t, 2H, JHP
21 Hz, PCH2P), 1.42 (s, 3H, Me2C), 1.31 (t, 3H, JHH
5 Hz, OCH2CH3), 1.27 (s, 3H, Me2C); 13C NMR
4.2.11. O0-Ethyl O0-(methyl-2,3-O-isopropylidene-b-D-
ribofuranosyl)[(diethoxyphosphinyl)-1-ethyl]phosphonate
8m. From 1b (320 mg), colorless oil, 266 mg (60%).