Xia et al.
H, J ) 6.0, 10.5 Hz, HB-6a), 3.89 (dd, 1 H, J ) 1.3, 9.8 Hz,
HC-3), 3.85-3.74 (m, 3 H, HA-6b, HA-6a, HC-2), 3.63 (d, 1 H,
HC-4), 3.55 (t, 1 H, HA-5), 3.48-3.42 (m, 1 H, HB-5), 3.31 (dd,
1 H, J ) 3.8, 9.9 Hz, HB-3), 2.04 (s, 3 H, Ac), 1.99 (s, 3 H, Ac),
1.86 (s, 3 H, Ac), 1.20 (d, 3 H, J ) 6.7 Hz, CH3). 13C NMR
(CDCl3, 100.6 MHz): δ 170.47 (CdO), 170.30 (CdO), 169.99
(CdO), 134.48, 132.74, 129.12, 128.70, 128.54, 128.47, 128.40,
128.30, 128.27, 128.15, 128.06, 128.01, 127.98, 127.73, 127.49,
127.43, 127.31, 126.84, 126.41, 125.93, 123.99, 100.03, 97.83,
84.65, 80.09, 79.92, 77.17, 75.31, 74.97, 74.54, 73.81, 73.71,
73.28, 72.66, 71.33, 70.92, 70.86, 68.28, 66.90, 65.93, 61.20,
55.90, 21.25 (Ac), 21.05 (Ac), 21.01 (Ac), 17.01 (CH3). Anal.
Calcd for C76H74O18NS: C, 69.07; H, 5.64; N, 1.06. Found: C,
70.35; H, 5.72; N, 1.07.
28 in quantitative yield as an amorphous solid. 1H NMR
(CDCl3, 600 MHz, DQF-COSY, TOCSY, and ROESY): δ 8.00-
7.00 (m, 31 H, ArH), 5.41-5.39 (m, 2 H, HD-4, J ) 2.8 Hz,
NHAc, J ) 9.4 Hz), 5.28 (d, 1 H, J ) 2.7 Hz, HA-4), 5.16 (d, 1
H, J ) 2.3 Hz, HB-4), 5.05-5.01 (m, 2 H, HA-2, HC-1, J 1,2 ) 8.8
Hz), 4.98-4.89 (m, 2 H, HD-2, HA-3), 4.81-4.73 (m, 4 H, HE-1,
C
10H7CHAO, PhCHAO, PhCH′AO, J gem ) 12. 3 Hz), 4.69-4.65
(m, 4 H, PhCH2O, HC-3, HE-5), 4.56 (d, 1 H, J gem ) 12.0 Hz,
10H7CHBO, ABq), 4.52 (d, 1 H, J 1,2 ) 7.7 Hz, HD-1), 4.48 (d,
C
1 H, J gem ) 12.4 Hz, PhCHBO, ABq), 4.46 (d, 1 H, J 1,2 ) 7.8
Hz, HA-1), 4.42 (d, 1 H, J gem ) 12.9 Hz, PhCH′′AO, ABq), 4.39-
4.28 (m, 3 H, HC-2, HB-2, PhCH′BO, J gem ) 12.1 Hz, ABq), 4.23
(d, 1 H, J gem ) 12.1 Hz, PhCH′′BO, ABq), 4.17-4.09 (m, 4 H,
HB-1, HC-4, HD-6b, HA-6b), 4.06-3.95 (m, 2 H, HA-6a, H-6a),
3.93-3.88 (m, 2 H, HB-6b, HE-3), 3.86-3.70 (m, 5 H, HC-6b,
HE-2, HB-5, HC-6a, HB-3), 3.62 (d, 1 H, J ) 2.8 Hz, HE-4), 3.51-
3.45 (m, 1 H, HC-5), 3.37 (t, 1 H, J ) 7.3, 7.4 Hz, HD-5), 3.28-
3.20 (m, 2 H, HB-6a, HD-3), 2.85 (s, 3 H, OCH3), 2.13 (s, 3 H,
Ac), 2.07 (s, 3 H, Ac), 2.06 (s, 3 H, Ac), 2.02 (s, 3 H, Ac), 2.00
(s, 3 H, Ac), 1.94 (s, 3 H, Ac), 1.92 (s, 3 H, Ac), 1.20 (d, 3 H, J
) 6.7 Hz, CH3), 1.15 (s, 9 H, t-Bu); 13C NMR (CDCl3, 100.6
MHz): δ 170.65 (CdO), 17.20 (CdO), 169.74 (CdO), 169.62
(CdO), 128.65, 128.42, 128.38, 128.30, 128.16, 128.08, 128.02,
127.97, 127.61, 127.32, 127.19, 126.54, 126.32, 101.28, 99.89,
99.14, 98.35, 97.53, 79.99, 77.01, 75.48, 75.16, 74.73, 74.42,
73.68, 73.66, 72.93, 72.54, 72.34, 71.61, 70.95, 70.82, 70.68
(2C), 69.98, 68.70, 68.00, 66.74, 66.68, 65.81, 61.05, 60.80,
56.57, 54.94, 48.92, 27.23 (3CH3), 23.63 (NHAc), 21.13 (Ac),
20.99 (Ac), 20.94 (Ac), 20.91 (Ac), 20.87 (Ac), 20.83 (Ac), 16.87
(CH3). Anal. Calcd for C98H111O34N2: C, 63.25; H, 6.01; N, 1.51.
Found: C, 63.25; H, 5.98; N, 1.46.
Meth yl
(3-O-Na p h th ylm eth yl-2,4,6-tr i-O-a cetyl-â-D-
ga la ct op yr a n osyl)-(1f4)-[(2,3,4-t r i-O-b e n zyl-r-L-fu co-
p yr a n osyl)-(1f3)]-6-O-ben zyl-2-d eoxy-2-p h th a lim id o-â-D-
glu cop yr a n osyl)-(1f6)-[(2,3,4,-tr i-O-a cetyl-6-O-tr im eth -
ylacetyl-â-D-galactopyranosyl)-(1f3)]-2-acetamido-2-deoxy-
r-D-ga la ctop yr a n osid e (27). A solution of acceptor 8 (50 mg.
0.082 mL), trisaccharide donor 7 (128 mg, 0.097 mmol), and
NIS (175 mg) in dry dichloromethane (4 mL) containing 4 Å
MS (2.0 g) was stirred at temperatures between -65 and -60
°C for 2 h under a N2 atmosphere. TfOH (17 µL) in dry
dichloromethane (0.5 mL) was added dropwise, and stirring
was continued at the same temperature for 1.5 h. Solids were
filtered off, and the filtrate was washed with saturated
NaHCO3 and 10% Na2SO3, dried (Na2SO4), and concentrated
to a crude residue that was passed through a column of silica
gel eluted with dichloromethane-methanol (60:1) to give a
1
pure compound 27 (113 mg, 76%) as an amorphous solid. H
NMR (CDCl3, 600 MHz, DQF-COSY, TOCSY, and ROESY):
δ 7.84-7.42 (m, 10 H, ArH), 7.40-6.84 (m, 21 H, ArH), 5.35
(d, 1 H, J ) 2.6 Hz, HA-4), 5.31 (d, 1 H, J ) 10.5 Hz, NHAc),
5.16-5.06 (m, 2 H, HB-2, HC-1, J 1,2 ) 8.6 Hz), 4.96-4.93 (m, 2
H, HD-2, HA-2), 4.81-4.75 (m, 3 H, HE-1, C10H7CHAO, Ph-
CHAO), 4.74-4.69 (m, 2 H, PhCHA′O, HC-3), 4.65 (m, 1 H, HE-
5), 4.56 (d, 1 H, J gem ) 12.3 Hz, PhCHBO, ABq), 4.53 (d, 1 H,
J 1,2 ) 8.3 Hz, HD-1), 4.50 (d, 1 H, J 1,2 ) 7.6 Hz, HA-1), 4.49 (d,
1 H, J gem ) 12.6 Hz, C10H7CHBO, ABq), 4.44 (d, 1 H,
PhCHA′′O), 4.43-4.30 (m, 4 H, HC-2, HB-2, PhCHA′′′O, Ph-
CHB′′O), 4.27 (d, 1 H, J gem ) 13.00 Hz, PhCHB′′′O, ABq), 4.18
(d, 1 H, J 1,2 ) 3.7 Hz, HB-1), 4.16-4.02 (m, 3 H, HD-6b, HC-4),
4.01-3.72 (m, 8 H, HD-6a, HB-6b, HE-3, HA-5, HB-4, HC-6b, HE-
2, HC-6a), 3.68-3.48 (m, 5 H, HB-5, HE-4, HB-6a, HB-3, HC-5),
3.39 (t, 1 H, HD-5), 3.24 (dd, 1 H, HD-3), 2.84 (s, 3 H, OCH3),
2.12 (s, 3 H, Ac), 2.05 (s, 3 H, Ac), 2.03 (s, 3 H, Ac), 1.99 (s, 3
H, Ac), 1.95 (s, 3 H, Ac), 1.91 (s, 3 H, Ac), 1.85 (s, 3 H, Ac),
1.20 (d, 3 H, J ) 6.1 Hz, CHE3), 1.15 (s, 9 H, t-Bu). 13C NMR
(CDCl3, 100.6 MHz): δ 170.38 (CdO), 17.30 (CdO), 170.25 (Cd
O), 170.20 (CdO), 169.52 (CdO), 169.50 (CdO), 169.39 (Cd
O), 168.40 (CdO), 139.10, 138.95, 138.20, 138.10, 135.10,
134.10, 129.35, 128.65, 128.41, 128.38, 128.31, 128.17, 128.11,
128.05, 128.00, 127.98, 127.62, 127.34, 127.31, 127.20, 126.69,
126.54, 126.37, 125.81, 101.91, 99.90, 99.24, 98.48, 97.49,
79.98, 78.00, 75.40, 75.31, 74.78, 74.43, 73.67, 72.92, 72.53,
72.30, 71.60, 71.08, 70.84, 70.71, 70.37, 68.92, 68.84, 66.97,
66.68, 65.58, 61.27, 61.06, 56.83, 54.83, 27.31, 21.14 (Ac), 20.95
(Ac), 20.93 (Ac), 20.89 (Ac), 20.80 (Ac), 20.74 (Ac), 20.67 (Ac),
18.85 (CH3). Anal. Calcd for C96H109O33N2: C, 63.39; H, 6.04;
N, 1.55. Found: C, 64.11; H, 6.08; N, 1.54.
Meth yl (2,4,6-Tr i-O-acetyl-â-D-galactopyr an osyl)-(1f4)-
[(2,3,4-tr i-O-ben zyl-r-L-fu copyr an osyl)-(1f3)]-6-O-ben zyl-
2-deoxy-2-ph th alim ido-â-D-glu copyr an osyl)]-(1f6)-[(2,3,4,-
tr i-O-a cetyl-6-O-tr im eth yla cetyl-â-D-ga la ctop yr a n osyl)-
(1f3)]-2-a c e t a m id o -4-O -a c e t y l-2-d e o x y -r-D -g a la c t o -
p yr a n osid e (29). A solution of compound 28 (167 mg) in a
mixture of dichloromethane-methanol-water (trace) (7 mL,
4:1) was added DDQ (28 mg), and the reaction mixture was
stirred at room temperature for 21 h. The mixture was
concentrated and taken up in dichloromethane (50 mL), which
was washed with saturated NaHCO3 (2 × 50 mL), dried (Na2-
SO4), and concentrated. The crude residue was applied to a
column of silica gel eluted with dichloromethane-ethyl acetate
(4:1) to give a pure compound 29 (66 mg, yield 58% based on
1
the recovery of 40 mg of starting material). H NMR (CDCl3,
600 MHz, DQF-COSY, TOCSY, and ROESY): δ 7.80-6.80 (m,
24 H, ArH), 5.38 (d, 1 H, J ) 9.1 Hz, NHAc), 5.29 (d, 1 H, J )
2.1 Hz, HA-4), 5.17 (d, 1 H, J ) 4.9 Hz, HB-4), 5.16 (d, 1 H, J
) 2.9 Hz, HD-4), 5.06-5.02 (m, 2 H, J ) 8.7 Hz, HC-1, HA-2),
4.92 (dd, 1 H, J ) 3.2, 10.3 Hz, HA-3), 4.84 (d, 1 H, J gem ) 12.3
Hz, PhCHAO, ABq), 4.79 (d, 1 H, J 1,2 ) 3.1 Hz, HE-1), 4.76 (d,
1 H, J gem ) 11.8 Hz, PhCHA′O, ABq), 4.75 (dd, 1 H, HD-2),
4.74 (dd 1 H, HD-2), 4.68 (t, 1 H, HC-3), 4.63 (d, 1 H, J 1,2 ) 8.8
Hz, HD-1), 4.58 (ddd, 1 H, HE-5), 4.55 (d, 1 H, J gem ) 12.3 Hz,
ArCHB′O, ABq), 4.51 (d, 1 H, J gem ) 12.1 Hz, ArCHA′′O, ABq),
4.47 (d, 1 H, HA-1), 4.45 (d, 1 H, J gem ) 12.8 Hz, ArCHBO, ABq),
4.41 (d, 1 H, J gem ) 11.8 Hz, ArCHA′′′O, ABq), 4.36 (t, 1 H,
HC-2), 4.32 (ddd, 1 H, HB-2), 4.22 (d, 1 H, J gem ) 12.4 Hz,
ArCHB′′′O, ABq), 4.16 (d, 1 H, J 1,2 ) 2.8 Hz, HB-1), 4.15-3.73
(m, 12 H, HB-6b, HA-6b, HD-6b, HA-6a, HC-6b, HB-6a, HD-6a,
HE-3, HC-6a, HE-2, HB-3), 3.60-3.20 (m, 5 H, HE-4, HC-5, HD-
5, HD-3), 2.87 (s, 3 H, OCH3), 2.14 (s, 3 H, Ac), 2.09 (s, 3 H,
Ac), 2.08 (s, 3 H, Ac), 2.02 (s, 3 H, Ac), 1.94 (s, 3 H, Ac), 1.93
(s, 3 H, Ac), 1.86 (s, 3 H, Ac), 1.16-1.13 (m, 12 H, t-Bu, CH3).
13C NMR (CDCl3, 100.6 MHz): δ 170.90 (CdO), 17.65 (CdO),
170.33 (CdO), 169.73 (CdO), 169.70 (CdO), 139.01, 134.25,
128.79, 128.51, 128.44, 128.37, 128.31, 128.18, 128.07, 127.64,
127.35, 127.20, 101.28, 99.37, 99.18, 98.36, 97.80, 80.00, 77.44,
75.47, 75.34, 74.72, 74.41, 73.78, 73.69, 73.10, 72.98, 72.88,
72.57, 71.33, 70.94, 70.82, 70.71, 69.99, 69.49, 68.97, 68.72,
68.00, 66.74, 66.64, 60.93, 60.80, 56.52, 54.76, 48.93, 27.23,
Meth yl
(3-O-Na p h th ylm eth yl-2,4,6-tr i-O-a cetyl-â-D-
galactopyranosyl)-(1f4)-[(2,3,4-tri-O-benzyl-r-L-fucopyranosyl)--
(1f3)]-6-O-b e n zy l-2-d e o x y -2-p h t h a lim id o -â-D -glu c o-
pyranosyl)]-(1f6)-[(2,3,4,-tri-O-acetyl-6-O-trimethylacetyl-â-D-
galactopyranosyl)-(1f3)]-2-acetamido-4-O-acetyl-2-deoxy-r-D-
ga la ctop yr a n osid e (28). A solution of compound 27 (223 mg)
was treated with anhydrous acetic anhydride (5 mL) and dry
pyridine (5 mL) in the presence of a catalytic amount of DMAP
(5 mg) at room-temperature overnight. The reaction mixture
was concentrated and applied to a column of silica gel eluted
with dichloromethane-ethanol (80:1) to give a pure compound
2758 J . Org. Chem., Vol. 68, No. 7, 2003