K. Glegoła et al. / Tetrahedron 63 (2007) 7133–7141
7139
6.97–6.94 (m, 1H, Harom), 6.12 (br d, J¼9.4 Hz, 1H, NH),
5.26 (dd, J¼10.0, 9.9 Hz, 1H, H-3), 5.11 (dd, J¼10.0,
9.9 Hz, 1H, H-4), 4.53 (d, J¼3.6 Hz, 1H, H-1), 4.45 (ddd,
J¼10.0, 9.4, 3.6 Hz, 1H, H-2), 4.21 (dd, J¼12.2, 4.5 Hz,
1H, H-6), 4.10 (dd, J¼12.2, 2.5 Hz, 1H, H-6), 3.90 (ddd,
J¼10.0, 4.5, 2.5 Hz, 1H, H-5), 3.30 (s, 3H, OMe), 2.09 (s,
3H, Me), 2.04 (s, 3H, Me), 2.02 (s, 3H, Me); 13C NMR
(75 MHz, CDCl3, 298 K): d 171.7, 171.1, 169.7, 168.9,
140.7 (d, J¼24.8 Hz), 137.9 (d, J¼11.2 Hz), 137.6 (d,
J¼11.2 Hz), 137.5 (d, J¼22.3 Hz), 134.8, 134.2 (d, J¼
8.5 Hz), 134.1 (d, J¼6.2 Hz), 131.0, 129.3, 129.1 (d,
J¼7.8 Hz), 128.9 (d, J¼7.8 Hz), 127.9 (d, J¼4.9 Hz),
98.6, 71.6, 68.6, 68.1, 62.4, 55.7, 52.3, 21.4, 21.2, 21.0;
31P NMR (121 MHz, CDCl3, 298 K): d ꢂ8.5 ppm; HRMS
(ESI) calcd for C32H35NO9P [M+H]+: 608.2050, found:
608.2072; calcd for C32H34NO9NaP [M+Na]+: 630.1869,
found: 630.1855.
4.2.5. Benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-{[2-(diphenyl-
phosphino)benzoyl]amino}-b-D-glucopyranoside 8b.
White solid (yield 65%); mp¼60–63 ꢀC; Rf¼0.84 (CHCl3/
MeOH 10/1); [a]D25 +29.5 (c 0.5, CHCl3); 1H NMR
(300 MHz, CDCl3, 298 K): d 7.42–7.20 (m, 18H, Harom),
7.06–7.02 (m, 1H, Harom), 5.84 (br d, J¼8.7 Hz, 1H, NH),
5.26 (dd, J¼10.3, 9.4 Hz, 1H, H-3), 5.10 (dd, J¼9.8,
9.4 Hz, 1H, H-4), 4.84 (d, J¼12.0 Hz, 1H, OCH2Ph), 4.67
(d, J¼8.3 Hz, 1H, H-1), 4.64 (d, J¼12.0 Hz, 1H, OCH2Ph),
4.27 (dd, J¼12.2, 4.5 Hz, 1H, H-6), 4.17 (dd, J¼12.2,
2.6 Hz, 1H, H-6), 4.16 (ddd, J¼10.3, 8.7, 8.3 Hz, 1H,
H-2), 3.64 (ddd, J¼9.8, 4.5, 2.6 Hz, 1H, H-5), 2.10 (s, 3H,
Me), 2.05 (s, 3H, Me), 2.01 (s, 3H, Me); 13C NMR
(75 MHz, CDCl3, 298 K): d 171.4, 171.2, 169.8, 169.3,
142.0 (d, J¼29.6 Hz), 137.9 (d, J¼11.5 Hz), 137.5 (d,
J¼10.4 Hz), 137.3, 136.5 (d, J¼21.4 Hz), 135.3, 134.2 (d,
J¼12.0 Hz), 134.0 (d, J¼8.8 Hz), 133.8 (d, J¼8.8 Hz),
130.7, 129.3, 129.0–128.3 (area with eight peaks), 127.6
(d, J¼6.0 Hz), 99.8, 72.6, 72.2, 71.0, 69.2, 62.5, 54.9,
21.5, 21.1, 21.0; 31P NMR (121 MHz, CDCl3, 298 K):
d ꢂ10.5 ppm; HRMS (ESI) calcd for C38H39NO9P
[M+H]+: 684.2363, found: 684.2357.
4.2.3. Methyl 3,4,6-tri-O-acetyl-2-deoxy-2-{[2-(diphenyl-
phosphino)benzoyl]amino}-b-D-glucopyranoside 7b.
White solid (yield 42%); mp¼129–131 ꢀC; Rf¼0.44
(CHCl3/MeOH 10/1); [a]2D5 +38.0 (c 0.5, CHCl3); 1H
NMR (300 MHz, CDCl3, 298 K): d 7.55–7.50 (m, 1H,
Harom), 7.40–7.20 (m, 12H, Harom), 6.99–6.94 (m, 1H,
Harom), 6.01 (br d, J¼8.2 Hz, 1H, NH), 5.34 (dd, J¼10.2,
9.6 Hz, 1H, H-3), 5.08 (dd, J¼9.6, 9.4 Hz, 1H, H-4), 4.59
(d, J¼8.5 Hz, 1H, H-1), 4.27 (dd, J¼12.0, 4.3 Hz, 1H,
H-6), 4.14 (dd, J¼12.0, 2.3 Hz, 1H, H-6), 4.00 (ddd,
J¼10.2, 8.5, 8.2 Hz, 1H, H-2), 3.70 (ddd, J¼9.4, 4.3,
2.3 Hz, 1H, H-5), 3.45 (s, 3H, OMe), 2.08 (s, 3H, Me),
2.05 (s, 3H, Me), 2.02 (s, 3H, Me); 13C NMR (75 MHz,
CDCl3, 298 K): d 171.2, 171.1, 169.9, 169.4, 142.0 (d, J¼
29.1 Hz), 137.6 (d, J¼11.2 Hz), 137.3 (d, J¼10.5 Hz),
136.1 (d, J¼21.0 Hz), 135.1, 134.1 (d, J¼7.2 Hz), 134.1
(d, J¼5.0 Hz), 134.0 (d, J¼6.2 Hz), 130.8, 129.4, 129.1 (d,
J¼6.8 Hz), 129.0 (d, J¼10.5 Hz), 128.9 (d, J¼8.1 Hz),
128.1 (d, J¼5.6 Hz), 101.8, 72.5, 72.1, 69.2, 62.5, 57.2,
55.2, 21.4, 21.2, 21.1; 31P NMR (121 MHz, CDCl3,
298 K): d ꢂ10.3 ppm; HRMS (ESI) calcd for C32H34NO9NaP
[M+Na]+: 630.1869, found: 630.1872.
4.3. General procedure for deprotection of the acet-
amido function
The three steps (Boc protection, deacetylation, and cleavage
of the Boc group) have been performed without intermediate
purification. The acetamido derivatives 12a,b or 13a,b
(1.15 mmol) and N,N-dimethyl-4-aminopyridine (28 mg,
0.23 mmol) were dissolved in THF (3 mL). Di-tert-butyl di-
carbonate (0.80 mL, 752 mg, 3.45 mmol) was added and the
mixture was refluxed for 14 h. The solution was cooled to rt,
methanol (3 mL) added, and the mixture treated with mono-
hydrate hydrazine (0.15 mL, 230 mg, 4.60 mmol) for 4 h.
The mixture was then poured into CH2Cl2 (10 mL), the or-
ganic solution washed with 1 M HCl, CuSO4, and NaHCO3
solutions, dried, and concentrated under reduced pressure.
CF3CO2H (6 mL) was added and the mixture stirred at
rt for 14 h. After evaporation, the residue was dissolved
in CH2Cl2 (10 mL) and washed with 10% Na2CO3
(2ꢁ5 mL). The aqueous phase was extracted with CH2Cl2
(3ꢁ5 mL), and the combined organic phases were dried
and concentrated under reduced pressure. The crude residue
was purified by column chromatography on silica gel to give
the corresponding amino derivatives 14a,b and 15a,b.
4.2.4. Benzyl 3,4,6-tri-O-acetyl-2-deoxy-2-{[2-(diphenyl-
phosphino)benzoyl]amino}-a-D-glucopyranoside 8a.
White solid (yield 53%); mp¼53–56 ꢀC; Rf¼0.80 (CHCl3/
MeOH 10/1); [a]D25 +70.0 (c 0.5, CHCl3); 1H NMR
(300 MHz, CDCl3, 298 K): d 7.40–7.20 (m, 18H, Harom),
7.00–6.90 (m, 1H, Harom), 6.18 (br d, J¼9.4 Hz, 1H, NH),
5.31 (dd, J¼10.3, 9.8 Hz, 1H, H-3), 5.14 (dd, J¼9.8,
9.8 Hz, 1H, H-4), 4.85 (d, J¼3.6 Hz, 1H, H-1), 4.66 (d,
J¼11.8 Hz, 1H, OCH2Ph), 4.50 (ddd, J¼10.3, 9.4, 3.6 Hz,
1H, H-2), 4.49 (d, J¼11.8 Hz, 1H, OCH2Ph), 4.20 (dd,
J¼12.2, 4.1 Hz, 1H, H-6), 4.01 (dd, J¼12.2, 2.2 Hz, 1H,
H-6), 3.95 (ddd, J¼9.8, 4.1, 2.2 Hz, 1H, H-5), 2.09 (s, 3H,
Me), 2.05 (s, 3H, Me), 2.02 (s, 3H, Me); 13C NMR
(75 MHz, CDCl3, 298 K): d 171.9, 171.1, 169.7, 168.9,
140.7 (d, J¼25.4 Hz), 137.7 (d, J¼12.4 Hz), 137.5 (d,
J¼10.5 Hz), 137.0, 134.9, 134.3, 134.0, 130.9, 129.2–
128.6 (area with nine peaks), 127.3 (d, J¼4.3 Hz), 97.2,
71.6, 70.7, 68.6, 68.5, 62.2, 52.2, 21.5, 21.1, 21.0; 31P
NMR (121 MHz, CDCl3, 298 K): d ꢂ8.6 ppm; HRMS
(ESI) calcd for C38H39NO9P [M+H]+: 684.2363, found:
684.2365; calcd for C38H38NO9NaP [M+Na]+: 706.2182,
found: 706.2176.
4.3.1. Methyl 3,4,6-tri-O-acetyl-2-amino-2-deoxy-a-D-
glucopyranoside 14a. Colorless oil (yield 40%); Rf¼0.57
(CHCl3/MeOH 10/1); [a]2D5 +141.5 (c 0.8, CHCl3); 1H
NMR (300 MHz, CDCl3, 298 K): d 5.12 (dd, J¼9.8,
9.8 Hz, 1H, H-3), 4.95 (dd, J¼9.8, 9.4 Hz, 1H, H-4), 4.76
(d, J¼3.5 Hz, 1H, H-1), 4.28 (dd, J¼12.2, 4.7 Hz, 1H,
H-6), 4.07 (dd, J¼12.2, 1.7 Hz, 1H, H-6), 3.96 (ddd,
J¼9.4, 4.7, 1.7 Hz, 1H, H-5), 3.42 (s, 3H, OMe), 2.93 (br
d, J¼7.9 Hz, 1H, H-2), 2.09 (s, 3H, Me), 2.07 (s, 3H, Me),
2.02 (s, 3H, Me), 1.53 (br, 2H, NH2); 13C NMR (75 MHz,
CDCl3, 298 K): d 171.1, 170.9, 170.0, 100.8, 70.0, 69.1,
67.8, 62.5, 55.7, 54.8, 21.1, 21.0, 20.9; Anal. Calcd for
C13H21NO8: C 48.90, H 6.62; found: C 48.83, H 6.53.
4.3.2. Methyl 3,4,6-tri-O-acetyl-2-amino-2-deoxy-b-
D-glucopyranoside 14b. White solid (yield 45%);