C. Gege, R.R. Schmidt / Carbohydrate Research 337 (2002) 1089–1094
1093
glucopyranosyl]-2,3-di-O-(2-decyl-dodecyl)-
D
-threitol
H), 3.88 (1%-CHH), 3.87 (4c-H), 3.86 (COOCH3), 3.84
(5e-H), 3.77 (4a-H), 3.73 (5b-H), 3.69 (3b-H), 3.63
(6f-H), 3.51 (5a-H), 3.45 (5c-H), 3.35 (2%-H), 3.34 (1%-
CHH), 3.18 (2c-H), 3.14, 3.07 (3%-CH2)], 2.58 (dd, J3,4
4.2, Jgem 12.4 Hz, 2 H, 3f-He), 2.20–1.85 (m, 108 H, 36
COCH3), 1.68 (t, J3,4=Jgem 12.3 Hz, 2 H, 3f-Ha), 1.62
(s, 2 H, 4%-H), 1.32–0.94 (m, 78 H, 36 CH2, 6d-CH3),
0.89 (t, 12 H, 4 CH3). 13C NMR (151 MHz, CDCl3,
excerpt): l 100.8 (1a-C), 100.7 (1b-C), 99.9 (1e-C), 99.4,
(1c-C), 95.3 (1d-C), 78.6 (2%-C), 76.0 (3b-C), 75.6 (4a-
C), 74.4 (3%-C), 74.3 (4c-C), 73.1 (5c-C), 72.8 (5a-C),
72.5 (3a-C), 72.3 (3c-C), 71.9 (6f-C), 71.8 (2a-C), 71.6
(4d-C), 71.4 (3e-C), 71.2 (2b-C), 71.2 (5b-C), 70.9 (5e-
C), 70.1 (1%-C), 69.8 (2e-C), 69.4 (4f-C), 69.0 (4b-C),
68.9 (2d-C), 68.0 (3d-C), 67.6 (8f-C), 67.4 (4e-C), 66.6
(7f-C), 64.1 (5d-C), 62.1 (6a-C), 61.7 (9f-C), 61.5 (6b-
C), 61.4 (6e-C), 60.9 (6b-C), 58.5 (2cC), 53.2 (OCH3),
49.1 (5f-C), 38.3 (4%-C), 37.4 (3f-C), 15.8 (6d-C).
MALDI-MS (positive mode, THF): 4598.7 [M+Na]+,
4613.1 [M+K]+. Anal. Calcd for C214H314N4O102
(4574.70): C, 56.19; H, 6.92; N, 1.22. Found: C, 56.20;
H, 6.84; N, 0.85.
(2).—To a solution of 12 (130 mg, 35.0 mmol) in dry
MeOH (40 mL) was added NaOMe (40 mg). The
mixture was stirred for 3 days at rt, then neutralized
with Amberlite IR-120 (H+), filtered, and adsorbed on
RP-18 Silica Gel. Flash chromatography with RP-18
Silica Gel (2:1–5:1–1:0 MeOH–water) furnished 2
(57.9 mg, 78%) as a colorless amorphous solid after
1
lyophilization from water. Rf 0.36 (MeOH, RP-18); H
NMR (600 MHz, CD3OD): l 5.05 (d, J1,2 3.8 Hz, 2 H,
1d-H), 4.82 (5d-H in solvent signal), 4.70 (d, J1,2 7.9 Hz,
2 H, 1c-H), 4.43 (d, J1,2 7.5 Hz, 2 H, 1e-H), 4.37 (d, J1,2
7.7 Hz, 2 H, 1b-H), 4.32 (d, J1,2 7.8 Hz, 2 H, 1a-H),
4.05–3.23 [m, 54 H, HMQC: 4.05 (4b-H), 3.95 (6%c-H),
3.91 (3c-H), 3.90 (2c-H), 3.90 (6c-H), 3.89 (6%a-H), 3.87
(4c-H), 3.86 (3d-H), 3.84 (6a-H), 3.79 (4e-H), 3.78
(6%b-H), 3.76 (6%e-H), 3.71 (4d-H), 3.67 (6b-H), 3.66
(6e-H), 3.64 (2d-H), 3.62 (2b-H), 3.58 (5b-H), 3.57
(4a-H), 3.53 (3b-H), 3.52 (3a-H), 3.50 (2e-H), 3.45
(5e-H), 3.45 (3e-H), 3.43 (5c-H), 3.40 (5a-H), 3.26 (2a-
H)], 1.97 (s, 6 H, COCH3), 1.55 (m, 2 H, 4%-H),
1.38–1.28 (m, 72 H, 36 CH2), 1.17 (d, J5,6 6.5 Hz, 6 H,
6d-CH3), 0.90 (t, 12 H, 4 CH3). MALDI-MS (positive
mode, MeOH): 2436.4 [M+Na]+.
1,4 - Di - O - [(triethylammonium - 5 - acetamido - 3,5 - di-
deoxy-
(23)-(i-
nosyl)-(13)]-(2-acetamido-2-deoxy-i-
nosyl) - (13) - (i - - galactopyranosyl) - (14) - i -
glucopyranosyl]-2,3-di-O-(2-decyl-dodecyl)- -threitol
D
-glycero-h-
D
-galacto-2-nonulopyranosylonate)-
-fucopyra-
-glucopyra-
D
-galactopyranosyl)-(14)-[(h-
L
1,4-Di-O-[(methyl-5-acetamido-4,7,8,9-tetra-O-ace-
D
tyl-3,5-dideoxy-
osylonate)-(23)-(2,4,6-tri-O-acetyl-i-
nosyl) - (14) - [(2,3,4 - tri - O-acetyl-h- -fucopyranosyl)-
(13)]-(2-acetamido-6-O-acetyl-2-deoxy-i- -gluco-
pyranosyl)-(13)-(2,4,6-tri-O-acetyl-i- -galactopyra-
nosyl)-(14)-3,6-di-O-acetyl-2-O-benzoyl-i- -gluco-
pyranosyl]-2,3-di-O-(2-decyl-dodecyl)- -threitol (14).—
D
-glycero-h-
D
-galacto-2-nonulopyran-
D
D-
D
-galactopyra-
D
L
(3).—To a solution of 14 (159 mg, 34.8 mmol) in dry
MeOH (40 mL) was added NaOMe (80 mg). The
mixture was stirred for 2 days at rt, then water (0.5 mL)
was added and stirred for 3 h. After neutralization with
Amberlite IR-120 (H+), the mixture was filtered and
adsorbed on RP-18 Silica Gel. Flash chromatography
with RP-18 Silica Gel (5:1–8:1–1:0 MeOH–water+
0.5% NEt3) afforded 1 (91.4 mg, 82%) as a colorless
amorphous solid after lyophilization from water. Rf
D
D
D
D
A solution of sLeX trichloroacetimidate 1313 (346 mg,
165 mmol, 3 equiv) and 4 (40.7 mg, 55.0 mmol) in dry
CH2Cl2 (5 mL) was stirred with molecular sieves AW-
300 for 30 min. Then TMSOTf (4.0 mL, 22 mmol, 0.4
equiv) was added under argon at rt and after 30 min
again TMSOTf (2.0 mL, 0.2 equiv). After further 4.5 h,
the solution was neutralized with NEt3, filtrated, and
concentrated. Flash chromatography (20:1–15:1
CHCl3–MeOH) of the residue gave 14 (166 mg, 66%)
as a colorless foam. [h]D −19.5° (c 1, CHCl3); Rf 0.26
1
0.71 (MeOH, RP-18); H NMR (600 MHz, CD3OD): l
5.04 (d, J1,2 3.7 Hz, 2 H, 1d-H), 4.82 (5d-H in solvent
signal), 4.68 (d, J1,2 7.7 Hz, 2 H, 1c-H), 4.50 (d, J1,2 7.7
Hz, 2 H, 1e-H), 4.37 (d, J1,2 7.7 Hz, 2 H, 1b-H), 4.32 (d,
J1,2 7.8 Hz, 2 H, 1a-H), 4.05–3.25 [m, 68 H, HMQC:
4.05 (4b-H), 4.03 (3e-H), 4.02 (6%c-H), 3.93 (2c-H), 3.91
(3c-H), 3.89 (6a-H), 3.87 (4e-H), 3.88 (6c-H), 3.85 (4c-
H), 3.84 (9%f-H), 3.84 (6a-H), 3.77 (6%b-H), 3.75 (6%e-H),
3.71 (4d-H), 3.70 (5f-H), 3.70 (4f-H), 3.69 (6f-H), 3.69
(6b-H), 3.64 (6e-H), 3.63 (7f-H), 3.62 (2d-H), 3.61
(2b-H), 3.59 (9f-H), 3.59 (5b-H), 3.57 (3d-H), 3.56
(4a-H), 3.54 (3b-H), 3.53 (2e-H), 3.51 (3a-H), 3.45
(8f-H), 3.45 (5e-H), 3.43 (5c-H), 3.39 (5a-H), 3.25 (2a-
H)], 3.20 (q, 12 H, N(CH2Me)3), 2.87 (dd, 2 H, 3f-He),
2.00, 1.97 (2 s, 12 H, 2 COCH3), 1.71 (t, 2 H, 3f-Ha),
1.55 (m, 2 H, 4%-H), 1.37–1.28 (m, 90 H, 18 CH2,
N(CH2CH3)3), 1.15 (d, J5,6 6.5 Hz, 6 H, 6d-CH3), 0.90
(t, 12 H, 2 CH3). MALDI-MS (negative mode, matrix
4-nitroaniline, MeOH): 2990 [M−NEt3−HNEt3]−,
3012 [M−2HNEt3+Na]−.
1
(3:2 toluene–acetone, HPTLC); H NMR (600 MHz,
CDCl3): l 8.00–7.42 (m, 10 H, 2 C6H5), 5.33–5.31 [m,
12 H, HMQC: 5.51 (8f-H), 5.44 (7f-H), 5.33 (1d-H),
5.33 (4b-H), 5.32 (NcH), 5.31 (4d-H)], 5.23 (dd, J2,3
=
J3,4 9.5 Hz, 2 H, 3a-H), 5.20 (dd, J2,3 10.9, J3,4 3.1 Hz,
2 H, 3d-H), 5.10 (dd, J1,2 8.2, J2,3 9.5 Hz, 2 H, 2a-H),
5.02–4.77 [m, 20 H, HMQC: 5.00 (5d-H), 4.98 (2b-H),
4.95 (4e-H), 4.95 (2d-H), 4.90 (1c-H), 4.89 (2e-H), 4.88
(4f-H), 4.81 (6%c-H), 4.77 (1e-H), NfH], 4.52 (dd, J2,3
10.1, J3,4 3.2 Hz, 2 H, 3e-H), 4.43–4.37 [m, 4 H,
HMQC: 4.42 (6%a-H), 4.38 (6%e-H)], 4.33 (d, J1,2 7.9 Hz,
2 H, 1a-H), 4.31 (d, J1,2 8.0 Hz, 2 H, 1b-H), 4.43–3.07
[m, 50 H, HMQC: 4.25 (9%f-H) 4.22 (3c-H), 4.22 (6e-H),
4.13 (6a-H), 4.08 (9f-H), 4.03 (5f-H), 4.00 (6b-H, 6%b-