A. Imberty, T. Kakuchi et al.
(dd, J=12.2, 5.6 Hz, 1H; H-6a), 4.20–4.05 (m, 2H; H-2, H-6b), 3.89
(ddd, J=9.8, 5.6, 2.5 Hz, 1H; H-5), 3.02 (s, 1H; CꢂCH), 2.07, 2.06,
2.05, 1.96 ppm (s, 12H; OAc); 13C NMR (CDCl3): d=170.9, 170.7,
170.6, 169.5 (C=O), 157.3, 133.6, 116.9 (Ar), 98.5 (C-1), 83.2 (Ar-Cꢂ
CH), 76.8 (Ar-CꢂCH), 72.1, 72.0, 68.7, 62.3, 54.8 (C-2, C-3, C-4, C-5, C-
6), 23.4, 20.8, 20.7 ppm (CH3); elemental analysis (%) calcd. for
C22H25NO9: C 59.06, H 5.63, N 3.13; found: C 58.86, H 5.63, N 2.98.
7.39, 6.98 (d, J=8.7 Hz, 4H; Ar), 5.35–5.39 (br, 2H; H-4, H-7), 5.25
(d, J=10.1 Hz, 1H; NH), 4.95 (ddd, J=12.2, 4.6, 4.5 Hz, 1H; H-8),
4.49 (d, J=10.8 Hz, 1H; H-6), 4.29–4.07 (m, 3H; H-5, H-9a, H-9b),
3.62 (s, 3H; OCH3), 2.70 (dd, J=13.0, 4.7, 1H; H-3e), 2.35 (m, 1H;
H-3a), 2.16, 2.13, 2.05, 1.92, 1.69 (s, 15H; OAc, NHAc), 0.23 ppm (s,
9H; TMS); 13C NMR (CDCl3): d=171.0, 170.7, 170.3, 170.2, 170,1 (C=
O), 168.1 (C-1), 154.2, 133.3, 119.2, 118.5 (Ar), 104.6 (Ar-CꢂC-TMS),
99.9 (C-2), 93.6 (Ar-CꢂC-TMS), 73.5 (C-6), 69.0 (C-8), 68.6 (C-4), 67.2
(C-7), 62.0 (C-9), 53.0 (OCH3), 49.4 (C-5), 38.4 (C-3), 23.3, 21.1, 20.9,
20.8 ppm (NHAc, OAc); elemental analysis (%) calcd. for
C31H41NO13Si: C 56.10, H 6.23, N 2.10; found: C 55.82, H 6.09, N
2.10.
4-(Trimethylsilylethynyl)phenyl O-(2,3,4,6-tetra-O-acetyl-b-d-gal-
actopyranosyl)-(1!4)-(O-2,3,6-tri-O-acetyl)-b-d-glucopyranoside:
Method A was applied to 4-iodophenyl O-(2,3,4,6-tetra-O-acetyl-b-
d-galactopyranosyl)-(1!4)-(O-2,3,6-tri-O-acetyl)-b-d-glucopyrano-
side (5.09 g, 6.08 mmol), bis(triphenylphosphine)palladium dichlor-
ide (86 mg, 120 mmol), copper(I) iodide (47 mg, 250 mmol), triethyl-
amine (21 mL), dry THF (24 mL), and trimethylsilylacetylene
(1.5 mL, 42 mmol). The product was purified by column chroma-
tography (silica gel, hexane/ethyl acetate 2:3, v/v) to give 4-(tri-
methylsilylethynyl)phenyl O-(2,3,4,6-tetra-O-acetyl-b-d-galactopyra-
nosyl)-(1!4)-(O-2,3,6-tri-O-acetyl)-b-d-glucopyranoside as a white
solid. Yield: 4.59 g (92%); 1H NMR (CDCl3): d=7.39, 6.89 (d, J=
8.6 Hz, 4H; Ar), 5.36 (d, J=3.2 Hz, 1H; H-1Glc), 5.28 (m, 1H; H-
1Gal), 5.20–5.05 (m, 3H; H-2Glc, H-2Gal, H-4Glc), 4.97 (m, 1H; H-
3Glc), 4.52–4.47 (m, 2H; H-4Gal, H-3Gal), 4.19–4.05 (m, 3H; H-5Glc,
H-6aGlc, H-6bGlc), 3.92–3.77 (m, 3H; H-5Gal, H-6aGal, H-6bGal)
2.16, 2.08, 2.07, 2.06, 2.06, 2.04, 1.97 (s, 21H; OAc) 0.24 ppm (s, 9H;
SiMe3); 13C NMR (CDCl3): d=170.5, 170.4, 170.2, 170.1, 169.8, 169.7,
169.2 (C=O), 156.8, 133.5, 118.2, 116.7 (Ar), 104.5 (Ar-CꢂC-SiMe3),
101.2 (C-1), 98.5 (C-1’), 93.6 (Ar-CꢂC-SiMe3), 76.3, 73.0, 72.9, 71.5,
71.0, 70.9, 69.2, 66.7, 62.1, 61.0 (C-2, C-2’, C-3, C-3’, C-4, C-4’, C-5, C-
5’, C-6, C-6’), 20.8–19.8 (CH3) 0.1 ppm (SiMe3); elemental analysis
(%) calcd. for C38H51O18Si: C 55.40, H 6.24; found: C 55.20, H 6.08.
Methyl (4-ethynylphenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-
dideoxy-d-glycero-a-d-galacto-2-nonulopyranosid)onate (PA-a-
NeuAc-OAc): Method B was applied to methyl [4-(trimethylsilyleth-
ynyl)phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d-glyc-
ero-a-d-galacto-2-nonulopyranosid]onate (2.93 g, 4.41 mmol), dry
CH2Cl2 (30 mL), and tetrabutylammonium fluoride (1.00 molLꢀ1 in
THF, 1.00 mL). The product was purified by column chromatogra-
phy (silica gel, hexane, CH2Cl2/MeOH 30:1!20:1, v/v) to give PA-a-
NeuAc-OAc as a white solid. Yield: 2.29 g (88%); 1H NMR (CDCl3):
d=7.41, 7.00 (d, J=8.2 Hz, 4H; Ar), 5.35–5.38 (br, 2H; H-4, H-7),
5.24 (d, J=10.0 Hz, 1H; NH), 4.95 (ddd, J=12.2, 4.9, 4.4 Hz, 1H; H-
8), 4.49 (d, J=8.2 Hz, 1H; H-6), 4.29–4.07 (m, 3H; H-5, H-9a, H-9b),
3.64 (s, 3H; OCH3), 3.03 (s, 1H; CꢂCH), 2.70 (dd, J=12.9, 4.9, 1H;
H-3e), 2.24 (m, 1H; H-3a), 2.16, 2.13, 2.05, 1.92, 1.67 ppm (s, 15H;
OAc, NHAc); 13C NMR (CDCl3): d=171.0, 170.6, 170.2, 170.1, 170,0
(C=O), 168.1 (C-1), 154.2, 133.4, 119.3, 117.4 (Ar), 99.8 (C-2) 83.1 (Ar-
CꢂCH) 76.7 (Ar-CꢂCH), 73.5 (C-6) 69.0 (C-8), 68.6 (C-4), 67.2 (C-7),
62.0 (C-9), 53.0 (OCH3), 49.4 (C-5), 38.3 (C-3), 23.2, 21.0, 20.8, 20.8,
20.7 ppm (NHAc, OAc); elemental analysis (%) calcd. for
C28H33NO13: C 56.85, H 5.62, N 2.37; found: C 56.55, H 5.54, N 2.20.
4-Ethynylphenyl
O-(2,3,4,6-tetra-O-acetyl-b-galactopyranosyl)-
(1!4)-(O-2,3,6-tri-O-acetyl)-b-d-glucopyranoside (PA-b-Lac-OAc):
Method B was applied to 4-(trimethylsilylethynyl)phenyl O-(2,3,4,6-
tetra-O-acetyl-b-d-galactopyranosyl)-(1!4)-(O-2,3,6-tri-O-acetyl)-b-
d-glucopyranoside (4.18 g, 5.19 mmol), CH2Cl2 (50 mL), and tetra-
butylammonium fluoride (6.22 mL; 1.00m in THF). The product was
purified by column chromatography (silica gel, hexane/ethyl ace-
tate 2:3, v/v) to give PA-b-Lac-OAc as a white solid. Yield: 3.20 g
Poly(4-ethynylphenyl 3,4,6,-tri-O-acetyl-2-N-acetyl-b-d-glucopyr-
anoside) (poly-PA-b-GlcNAc-OAc): A solution of Rh(norbornadi-
ene)BPh4 (12 mg, 22 mmol) in dry CHCl3 (3.0 mL) was added under
argon to
a stirred solution of PA-b-GlcNAc-OAc (500 mg,
1.12 mmol) in dry CHCl3 (8.0 mL). After 20 h at 308C, the reaction
was terminated by addition of triphenylphosphine (39 mg,
150 mmol) and the mixture was then poured into a large amount
of methanol. The precipitate was filtered off and dried in vacuo to
1
(84%); H NMR (CDCl3): d=7.42, 6.92 (d, J=8.9 Hz, 4H; Ar), 5.36 (d,
J=2.8 Hz, 1H; H-1Glc), 5.29 (m, 1H; H-1Gal), 5.21–5.06 (m, 3H; H-
2Glc, H-2Gal, H-4Glc), 4.97 (m, 1H; H-3Glc), 4.53–4.47 (m, 2H; H-
4Gal, H-3Gal), 4.19–4.05 (m, 3H; H-5Glc, H-6aGlc, H-6bGlc), 3.93–
3.77 (m, 3H; H-5Gal, H-6aGal, H-6bGal), 3.03 (s, 1H; CꢂCH), 2.16,
2.08, 2.07, 2.06, 2.06, 2.04, 1.97 ppm (s, 21H; OAc); 13C NMR
(CDCl3): d=170.4, 170.3, 170.2, 170.1, 169.8, 169.6, 169.2 (C=O),
157.0, 133.7, 117.0, 116.8 (Ar), 101.2, 98.4 (C-1, C-1’), 83.1 (Ar-CꢂCH),
76.8 (Ar-CꢂCH), 76.3, 73.0, 72.8, 71.5, 71.0, 70.8, 69.2, 66.7, 62.1,
60.9 (C-2, C-2’, C-3, C-3’, C-4, C-4’, C-5, C-5’, C-6, C-6’), 20.7–
20.6 ppm (CH3); elemental analysis (%) calcd. for C35H43O18: C 55.92,
H 5.77; found: C 55.52, H 5.58.
give PA-a-Neu-OAc as a yellow powder. Yield: 490 mg; Mnn, SEC
=
1.34ꢁ105; Mw/Mnn, SEC =10.1; IR (KBr): n˜ =1746 cmꢀ1 (nC O).
=
Poly[4-ethynylphenyl O-(2,3,4,6-tetra-O-acetyl-b-galactopyrano-
syl)-(1!4)-(O-2,3,6-tri-O-acetyl)-b-d-glucopyranoside] (poly-PA-
b-Lac-OAc): [Rh(nbd)Cl]2 (3.1 mg, 6.7 mmol) and triethylamine
(950 mL, 6.8 mmol) were added under argon to a stirred solution of
PA-b-Lac-OAc (500 mg, 680 mmol) in dry CHCl3 (6.1 mL). After stir-
ring for 20 h at 308C, the reaction was terminated by addition of
an excess quantity of acetic acid, and the mixture was then poured
into a large amount of methanol. The precipitate was filtered off
and dried in vacuo to give poly-PA-b-Lac-OAc as a yellow powder.
Yield: 330 mg; Mn, SEC =7.81ꢁ104; Mw/Mnn, SEC =3.79; IR (KBr): n˜ =
Methyl [4-(trimethylsilylethynyl)phenyl 5-acetamido-4,7,8,9-
tetra-O-acetyl-3,5-dideoxy-d-glycero-a-d-galacto-2-nonulopyra-
nosid]onate: Method B was applied to methyl (4-iodophenyl 5-
acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d-glycero-a-d-galacto-
2-nonulopyranosid)onate (3.35 g, 4.83 mmol), bis(triphenylphos-
phine)palladium dichloride (70.2 mg, 100 mmol), copper(I) iodide
(38.1 mg, 200 mmol), triethylamine (15 mL), dry THF (15 mL), and
trimethylsilylacetylene (1.4 mL, 10 mmol). The product was purified
by column chromatography (silica gel, CH2Cl2/MeOH 30:1!20:1, v/
v) to give methyl(4-trimethylsilylethynylphenyl 5-acetamido-4,7,8,9-
tetra-O-acetyl-3,5-dideoxy-d-glycero-a-d-galacto-2-nonulopyrano-
1740 cmꢀ1 (nC O).
=
Poly[methyl
(4-ethynylphenyl
5-acetamido-4,7,8,9-tetra-O-
acetyl-3,5-dideoxy-d-glycero-a-d-galacto-2-nonulopyranosid)o-
nate] (poly-PA-a-NeuAc-OAc): A solution of Rh(norbornadiene)-
BPh4 (7.0 mg, 14 mmol) in dry THF (800 mL) was added under argon
to a stirred solution of PA-a-NeuAc-OAc (400 mg, 680 mmol) in dry
THF (6.0 mL). After 20 h at 308C, the reaction was terminated by
addition of triphenylphosphine (21 mg, 80 mmol), and the mixture
was then poured into a large amount of diethyl ether. The precipi-
1
sid)onate as a white solid. Yield: 3.12 g (97%); H NMR (CDCl3): d=
2406
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemBioChem 2010, 11, 2399 – 2408