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M. Hollinger et al. / Carbohydrate Research 346 (2011) 1454–1466
5.10–5.06 (m, 2H, H-1II, H-1III), 4.71–4.55 (m, 3H, H-6aII, H-6a,bIII),
4.44 (dd, J2,3 12.7 Hz, J3,4 9.7 Hz, 1H, H-3III), 4.41–4.34 (m, 4H, H-
4I, H-6bII, H-5II, H-5III), 4.17 (dd, J2,3 10.5 Hz, J3,4 2.8 Hz, 1H, H-3I),
4.00–3.94 (m, 2H, H-6aI, H-5I), 3.82–3.75 (m, 2H, H-2I, H-2III), 3.72
(m, 1H, H-6bI), 2.99 (d, J 1.8 Hz, 1H, OH-4I), 2.49 (s, 3H, COCH3);
13C NMR (125 MHz, CDCl3) d 170.7 (COCH3), 166.0, 165.9, 165.6,
165.6, 165.3 and 165.3 (COC6H5), 161.4 (OC6H4NO2), 152.9 (CONC-
OCH3), 143.1 (OC6H4NO2), 133.9, 133.7, 133.5 and 133.4 (C6H5),
133.3 (2C, C6H5), 130.1 (2C, C6H5), 129.9 (2C, C6H5), 129.9 (2C,
C6H5), 129.8 (2C, C6H5), 129.8 (2C, C6H5), 129.7 (2C, C6H5), 129.5,
129.2, 129.2 and 128.9 (C6H5), 128.7 (2C, C6H5), 128.7 (2C, C6H5),
128.6 and 128.6 (C6H5), 128.6 (2C, C6H5), 128.6 (2C, C6H5), 128.3
(2C, C6H5), 128.3 (2C, C6H5), 125.7 (2C, OC6H4NO2), 117.0 (2C,
OC6H4NO2), 102.3 (C-1III), 100.0 (C-1II), 97.8 (C-1I), 78.4 (C-3I),
77.9 (C-5III), 74.6 (C-3III), 72.0 (C-5II), 71.6 (C-3II), 70.9 (C-4III), 69.4
(C-2II), 69.3 (C-5I), 68.1 (C-4II), 67.6 (C-4I), 66.8 (C-6I), 65.1 (C-6III),
62.1 (C-6II), 60.6 (C-2III), 57.9 (C-2I), 24.6 (COCH3). ES-HRMS calcd
for C69H59N5O24 [Na]+ 1364.3448, found 1364.3481.
10 mL CH2Cl2 containing 4 Å MS was stirred under a N2 atmo-
sphere at room temperature for 20 min. The mixture was cooled
to 0 °C, DMTST (0.136 g, 0.525 mmol) was added and the reaction
mixture was stirred for 1 h and during the time allowed to warm
up to room temperature. When no starting was left the reaction
was quenched by the addition of Et3N (200 lL) and diluted with
CH2Cl2 (50 mL), filtered through Celite and the filtrate was washed
with satd aq NaHCO3 (25 mL), 1 M HCl (25 mL) and satd aq NaH-
CO3 (25 mL), dried over MgSO4 and filtered. The solvent was evap-
orated and the crude product was purified by FC on silica gel
(toluene–EtOAc 5:1) to afford 38 (0.131 g, 72%) as a white solid:
Rf 0.54 (toluene–EtOAc 2:1); ½a D20
ꢂ
+105 (c 0.75, CHCl3). 1H NMR
(500 MHz, CDCl3) d 8.21–8.13 (m, 4H, OC6H4NO2, C6H5), 8.08–
8.03 (m, 2H, C6H5), 7.95–7.91 (m, 2H, C6H5), 7.65–7.59 (m, 2H,
C6H5), 7.57–7.45 (m, 5H, C6H5), 7.39–7.34 (m, 2H, C6H5), 7.23–
7.18 (m, 2H, OC6H4NO2), 5.67 (d, J1,2 3.5 Hz, 1H, H-1I), 5.62 (dd,
J2,3 11.0 Hz, J3,4 2.8 Hz, 1H, H-3I), 5.58 (dd, J 9.7, 3.7 Hz, 1H, H-4II),
5.17 (d, J1,2 6.5 Hz, 1H, H-1II), 4.77–4.67 (m, 2H, H-6a,bII), 4.55–
4.48 (m, 2H, H-3II, H-4I), 4.43–4.38 (m, 1H, H-5II), 4.22 (dd, J6a,6b
9.8 Hz, J5,6a 5.9 Hz, 1H, H-6aI), 4.14–4.09 (m, 2H, H-5I, H-2II), 4.06
(dd, J2,3 11.0 Hz, J1,2 3.5 Hz, 1H, H-2I), 3.75 (d, J 2.6 Hz, 1H, OH-
4I), 3.71 (dd, J 9.8, 3.4 Hz, 1H, H-6bI), 2.51 (s, 3H, COCH3). 13C
NMR (125 MHz, CDCl3) d 171.5 (COCH3), 166.8, 166.0 and 165.4
(COC6H5), 161.3 (OC6H4NO2), 152.9 (CONCOCH3), 143.2 (OC6H4-
NO2), 134.2, 133.8 and 133.7 (C6H5), 130.3 (2C, C6H5), 130.2 (2C,
C6H5), 129.9 (2C, C6H5), 129.6 and 129.4 (C6H5), 128.8 (2C, C6H5),
128.8 (2C, C6H5), 128.8 (3C, C6H5), 126.1 (2C, OC6H4NO2), 116.8
(2C, OC6H4NO2), 100.3 (C-1II), 97.4 (C-1I), 78.4 (C-5II), 74.9 (C-3II),
71.3 (C-3I), 70.8 (C-4II), 69.5 (C-5I), 68.2 (C-4I), 67.7 (C-6I), 65.6
(C-6II), 60.7 (C-2II), 57.4 (C-2I), 24.6 (COCH3). ES-HRMS calcd for
4.15. p-Nitrophenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-
b-
limido-b-
pyranoside (37)
D
-glucopyranosyl-(1?3)-3,4,6-tri-O-acetyl-2-deoxy-2-phtha-
D
-glucopyranosyl-(1?6)-2-azido-2-deoxy- -galacto-
a-D
To a solution of 33 (0.100 g, 0.134 mmol), donor 2617 (0.097 g,
0.202 mmol) and NIS (0.067 g, 0.296 mmol) in dry CH2Cl2
(2.4 mL) was added 4 Å MS and the mixture was stirred under a
N2 atmosphere at room temperature for 20 min. The mixture was
cooled to ꢀ30 °C, TMSOTf (2.4
lL, 0.013 mmol) was added and
the reaction mixture was stirred for 1 h. Thereafter the mixture
was diluted with CH2Cl2 (50 mL), filtered through Celite and the fil-
trate was washed with satd aq Na2S2O3 (50 mL), satd aq NaHCO3
(50 mL) and water (50 mL), dried over MgSO4 and concentrated.
The crude product was purified by FC on silica gel (toluene–EtOAc
2:1) to afford 37 (0.080 g, 51%) as a white solid: Rf 0.39 (toluene–
C
42H37N5O16 [Na]+ 890.2133, found 890.2158.
4.17. p-Nitrophenyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-
a-D-
galactopyranosyl-(1?6)-2-azido-3-benzoyl-2-deoxy-a-D-
galactopyranoside (39)
EtOAc 1:1); ½a 2D0
ꢂ
+125 (c 0.75, CHCl3). 1H NMR (600 MHz, CDCl3)
d 8.13–8.09 (m, 2H, OC6H4NO2), 7.91–7.83 (m, 4H, Phth), 7.81–
7.77 (m, 2H, Phth), 7.75–7.71 (m, 2H, Phth), 6.99–6.96 (m, 2H,
OC6H4NO2), 5.77 (dd, J2,3 10.7 Hz, J3,4 9.1 Hz, 1H, H-3II), 5.70 (dd, J
10.6, 9.1 Hz, 1H, H-3III), 5.59 (d, J1,2 8.5 Hz, 1H, H-1II), 5.36 (d, J1,2
8.5 Hz, 1H, H-1III), 5.30 (d, J1,2 3.5 Hz, 1H, H-1I), 5.16–5.06 (m, 2H,
H-4II, H-4III), 4.40 (dd, J2,3 10.7 Hz, J1,2 8.5 Hz, 1H, H-2II), 4.28–
4.19 (m, 4H, H-6aIII, H-6a,bII, H-2III), 4.15 (dd, J6a,6b 12.2 Hz, J5,6b
2.3 Hz, 1H, H-6bIII), 4.12–4.09 (m, 1H, H-4I), 4.05–3.99 (m, 2H, H-
6aI, H-3I), 3.92–3.87 (m, 1H, H-5I), 3.83–3.75 (m, 2H, H-5III, H-5II),
3.70 (dd, J6a,6b 10.5 Hz, J5,6b 7.0 Hz, 1H, H-6bI), 3.61 (dd, J2,3
10.5 Hz, J1,2 3.5 Hz, 1H, H-2I), 2.81 (dd, J 3.2 Hz, J 1.2 Hz, 1H, OH-
4), 2.13, 2.11, 2.07, 2.02, 1.87 and 1.84 (6s, 18H, COCH3). 13C
NMR (150 MHz, CDCl3) d 170.7, 170.6, 170.1, 170.1, 169.4 and
169.3 (COCH3), 168.0 (2C, Phth), 167.8 (2C, Phth), 161.2 and
143.2 (OC6H4NO2), 134.7 (2C, Phth), 134.4 (2C, Phth), 131.4 (2C,
Phth), 131.3 (2C, Phth), 125.8 (2C, OC6H4NO2), 123.7 (4C, Phth),
117.0 (2C, OC6H4NO2), 98.7 (C-1II), 98.2 (C-1III), 97.5 (C-1I), 78.2
(C-3I), 72.3 (C-5II), 72.1 (C-5III), 70.7 (C-3III), 70.4 (C-3II), 69.7 (C-
5I), 68.9 (C-4III), 68.7 (C-4II), 68.3 (C-6I), 67.3 (C-4I), 62.0 (C-6III),
61.8 (C-6II), 57.8 (C-2I), 54.6 (C-2III), 54.4 (C-2II), 20.8, 20.7, 20.6,
20.6, 20.4 and 20.4 (COCH3). Due to very broad peaks carbonyl car-
bons of the phthalimido group were determined by HMBC. ES-
HRMS calcd for C52H52N6O25 [Na]+ 1183.2880, found 1183.2888.
A solution of compound 21 (100 mg, 0.232 mmol) and trichloro-
acetimidate 17 (155 mg, 0.325 mmol) in dry CH2Cl2 (10 mL) con-
taining 4 Å MS was stirred under a N2 atmosphere at room
temperature for 20 min and then cooled to ꢀ20 °C. TMSOTf
(4.2 lL, 0.023 mmol) was added and the reaction mixture was stir-
red for 1 h until no starting material was left (monitored by TLC).
The mixture was diluted with CH2Cl2, filtered through Celite and
the filtrate was washed with 1 M HCl (50 mL) and satd aq NaHCO3
(50 mL), dried over MgSO4 and concentrated. The crude product
was purified by FC on silica gel (toluene–EtOAc 5:1) to afford the
a/b (5:1) mixture 39 (0.152 g, 88%) as a white solid. The pure a
anomer could be obtained by additional FC on silica gel (tolu-
ene–CH3CN 4:1?3:1). Rf 0.43 (toluene–CH3CN 3:1); ½a D20
ꢂ
+242 (c
0.74, CHCl3). 1H NMR (500 MHz, CDCl3) d 8.29–8.24 (m, 2H, OC6H4-
NO2), 8.14–8.10 (m, 2H, C6H5), 7.65–7.61 (m, 1H, C6H5), 7.53–7.47
(m, 2H, C6H5), 7.26–7.22 (m, 2H, OC6H4NO2), 5.84 (d, J1,2 3.4 Hz, 1H,
H-1I), 5.73 (dd, J 11.0, 3.0 Hz, 1H, H-3I), 5.43–5.40 (m, 1H, H-4II),
5.12 (dd, J2,3 11.1 Hz, J3,4 3.2 Hz, 1H, H-3II), 4.99 (d, J1,2 3.5 Hz, 1H,
H-1II), 4.47–4.44 (m, 1H, H-4I), 4.27–4.12 (m, 4H, H-5I, H-5II, H-2I,
H-6aI), 4.05–3.95 (m, 2H, H-6bI, H-6aII), 3.72 (dd, J6a,6b 10.7 Hz,
J5,6b 4.5 Hz, 1H, H-6bII), 3.68 (dd, J2,3 11.1 Hz, J1,2 3.5 Hz, 1H, H-
2II), 2.67 (d, J 3.2 Hz, 1H, OH-4), 2.13, 2.04, and 2.03 (3s, 9H,
COCH3). 13C NMR (125 MHz, CDCl3) d 170.7, 170.1 and 169.8
(COCH3), 165.7 (COC6H5), 160.9 and 143.6 (OC6H4NO2), 134.1
(C6H5), 130.2 (2C, C6H5), 129.2 (C6H5), 128.9 (2C, C6H5), 126.2
(2C, OC6H4NO2), 116.8 (2C, OC6H4NO2), 98.0 (C-1II), 97.2 (C-1I),
71.3 (C-3I), 70.2 (C-5I), 68.6 (C-3II), 67.7 (C-4I), 67.6 (C-4II), 67.1
(C-5II), 67.1 (C-6II), 61.9 (C-6I), 57.6 (C-2II), 57.5 (C-2I), 20.9, 20.8
and 20.7 (COCH3). ES-HRMS calcd for C31H33N7O15 [Na]+
766.1932, found 766.1945.
4.16. p-Nitrophenyl 2-acetamido-4,6-di-O-benzoyl-2,3-N,O
-carbonyl-2-deoxy-b-
D-glucopyranosyl-(1?6)-2-azido-3-O-
benzoyl-2-deoxy- -galactopyranoside (38)
a
-D
A solution of compound 21 (0.105 g, 0.210 mmol), donor 24
(0.136 g, 0.315 mmol) and DTBMP (0.129 g, 0.631 mmol) in