M. N. Amin et al. / Tetrahedron 63 (2007) 8181–8198
8195
[a]2D4 +70.96 (c 3.05, CH2Cl2); 1H NMR (CDCl3, 400 MHz):
d 1.06 (d, J¼5.6 Hz, H-6Bac, 3H), 1.10 (s, t-Bu, 9H), 1.94 (s,
CH3CO, 3H), 2.77 (qd, J¼5.6, 9.2 Hz, H-5Bac, 1H), 3.05–
3.18 (m, H-6aGalNIII, H-4Bac, H-6bGalNIII, H-6aGalNII, 4H),
3.29–3.33 (m, H-2Bac, H-3Bac, 2H), 3.40–3.56 (H-2Glc, H-
73.44, 73.56, 74.54, 74.82, 74.99, 75.39, 75.63, 75.92,
77.48, 78.09, 81.77, 84.58, 96.76, 98.87, 98.88, 98.91,
103.51, 126.91, 127.20, 127.23, 127.29, 127.40, 127.44,
127.53, 127.61, 127.66, 127.79, 127.85, 127.90, 128.03,
128.15, 128.19, 128.23, 128.26, 128.36, 128.40, 129.64,
129.83, 132.32, 132.89, 135.64, 135.70, 137.32, 137.35,
137.41, 137.48, 137.67, 137.80, 137.94, 138.25, 138.30;
MALDI-TOF MS: [M+Na]+ calcd for C109H119N15O20SiNa
2008.84, found 2009.75; HRMS ESI-TOF: [M+Na]+ calcd
for C109H119N15O20SiNa 2008.8423, found 2008.8446.
6bGalNII, H-2GalNIII, 3H), 3.59–3.74 (m, H-3Glc, H-2GalNI
,
H-2GalNII, H-6aGalNI, H-6bGalNI H-6aGlc, 6H), 3.82–3.96
(m, H-4Glc, H-6bGlc, H-3GalNI, H-3GalNII, 4H), 3.99–4.23
(m, H-5Glc, H-3GalNIII, H-5GalNI, H-5GalNII, 4H), 4.27–4.41
(m, H-1Bac, H-4GalNII, H-4GalNI, H-5GalNIII, PhCH2, 6H),
4.45–4.56 (m, PhCH2, 7H), 4.64–4.71 (m, H-1Glc, PhCH2,
3H), 4.74–4.98 (m, PhCH2, 7H), 5.05 (d, J¼3.6 Hz,
H-1GalNII, 1H), 5.11 (d, J¼3.6 Hz, H-1GalNIII, 1H), 5.23 (d,
Anal. Calcd for C109H119N15O20Si: C, 65.88; H, 6.04; N,
10.57. Found: C, 65.85; H, 6.15; N, 10.45.
J¼3.6 Hz, H-1GalNI, 1H), 5.63 (d, J¼2.0 Hz, H-4GalNIII
,
1H), 7.14–7.40 (m, Ar, 51H), 7.63–7.67 (m, Ar, 4H); 13C
NMR (CDCl3, 100 MHz): d 17.81, 19.13, 20.96, 26.82,
59.63, 59.74, 60.15, 66.38, 66.56, 67.47, 68.10, 68.27,
68.54, 68.92, 68.27, 68.54, 68.92, 69.01, 69.45, 70.32,
70.89, 71.67, 71.75, 71.82, 71.98, 72.94, 73.30, 73.39,
73.51, 74.77, 74.93, 75.28, 75.42, 77.51, 78.03, 82.18,
84.47, 96.73 (2ꢀC-1), 98.85 (2ꢀC-1), 103.39, 126.90,
127.16, 127.22, 127.27, 127.32, 127.37, 127.47, 127.51,
127.60, 127.79, 127.87, 127.98, 128.03, 128.06, 128.17,
128.21, 128.29, 128.38, 128.43, 129.67, 129.87, 132.31,
132.89, 135.67, 135.72, 137.29, 137.48, 137.66, 138.08,
138.37, 138.42, 138.58, 169.28; MALDI-TOF MS:
[M+Na]+ calcd for C111H121N15O21SiNa 2050.85, found
2050.63; HRMS ESI-TOF: [M+Na]+ calcd for
C111H121N15O21SiNa 2050.8528, found 2050.8522.
4.31. tert-Butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-
deoxy-4-O-pentafluoropropionyl-a-D-galactopyranosyl-
(1/4)-[2,3,4,6-tetra-O-benzyl-b-D-glucopyranosyl-
(1/3)]-2-azido-6-O-benzyl-2-deoxy-a-D-galactopyra-
nosyl-(1/4)-2-azido-3,6-di-O-benzyl-2-deoxy-a-D-gal-
actopyranosyl-(1/4)-2-azido-3,6-di-O-benzyl-2-deoxy-
a-D-galactopyranosyl-(1/3)-2,4-diazido-2,4,6-tri-
deoxy-b-D-glucopyranoside (18)
This compound was synthesized from compound 5 (1.171 g,
0.590 mmol) and 3a (0.449 g, 0.842 mmol) according to the
procedure described in Section 4.3 (1.310 g, 89%).
[a]2D4 +156.90 (c 0.36, CH2Cl2); 1H NMR (CDCl3,
400 MHz): d 1.09 (d, J¼6.0 Hz, H-6Bac, 3H), 1.12 (s, t-Bu,
9H), 2.79 (qd, J¼6.0, 9.2 Hz, H-5Bac, 1H), 3.05–3.12 (m,
H-6aGalNIII, H-4Bac, H-3Bac, H-6aGalNIV, 4H), 3.15 (dd,
J¼3.6, 10.4 Hz, H-2GalNIV, 1H), 3.21 (dd, J¼5.2, 8.4 Hz,
H-6aGalNII, 1H), 3.31–3.35 (m, H-2GalNII, H-2Bac, 2H),
3.50–3.58 (m, H-2Glc, H-6aGalNI, H-6bGalNIII, H-6aGlc, 4H),
4.30. tert-Butyldiphenylsilyl 2,3,4,6-tetra-O-benzyl-b-D-
glucopyranosyl-(1/3)-2-azido-6-O-benzyl-2-deoxy-a-
D-galactopyranosyl-(1/4)-2-azido-3,6-di-O-benzyl-2-
deoxy-a-D-galactopyranosyl-(1/4)-2-azido-3,6-di-O-
benzyl-2-deoxy-a-D-galactopyranosyl-(1/3)-2,4-dia-
zido-2,4,6-trideoxy-b-D-glucopyranoside (5)
3.63–3.69 (m, H-2GalNI, H-2GalNIII, H-3GalNGlc, H-6bGalNII
4H), 3.73–3.79 (m, H-6bGlc, H-6bGalNIV, H-4Glc, 3H), 3.82–
4.00 (m, H-3GalNIII, H-6bGlc,H-3GalNI, H-5Glc, H-3GalNIV
,
,
The title compound was obtained from compound 17
in quantitative yield upon deprotection of pentafluoropro-
pionyl ester by NaOMe according to the procedure described
for 14.
5H), 4.01–4.10 (m, H-3GalNII, PhCH2, 3H), 4.21 (m, H-5GalNI
,
1H), 4.30–4.37 (m, H-1Bac, H-5GalNII, H-5GalNIII, 3H), 4.37–
4.45 (m, H-4GalNIII, H-4GalNI, H-4GalNII, 3H), 4.48–4.58 (m,
PhCH2, 10H), 4.66 (d, J¼7.6 Hz, H-1Glc, 1H), 4.69–4.81
(m, H-5GalNIV, PhCH2, 7H), 4.83 (d, J¼4.0 Hz, H-1GalNIV
,
[a]2D6 +133.13 (c 0.68, CH2Cl2); 1H NMR (CDCl3,
400 MHz): d 1.07 (d, J¼6.0 Hz, H-6Bac, 3H), 1.10 (s, t-Bu,
9H), 2.78 (qd, J¼6.0, 8.8 Hz, H-5Bac, 1H), 3.03–3.11 (m,
1H), 4.85–4.95 (m, PhCH2, 4H), 5.12 (br s, H-1GalNII
,
H-1GalNIII, 2H), 5.25 (d, J¼4.0 Hz, H-1GalNI, 1H), 5.78 (br
s, H-4GalNIV, 1H), 7.06–7.45 (m, Ar, 61H), 7.65–7.69 (m,
Ar, 4H); 13C NMR (CDCl3, 100 MHz): d 17.93, 19.24,
26.93, 59.46, 59.56, 59.70, 59.76, 65.84, 66.28, 66.55,
66.61, 67.54, 68.70, 68.86, 68.97, 69.05, 69.43, 70.96,
71.20, 71.62, 71.68, 72.01, 72.94, 73.14, 73.59, 73.73,
73.83, 74.22, 75.05, 75.41, 75.81, 76.54, 78.12, 81.90,
84.68, 96.74, 96.96, 98.85, 98.89, 99.10, 105.84, 126.95,
127.19, 127.23, 127.33, 127.43, 127.59, 127.65, 127.70,
127.81, 127.84, 127.95, 127.99, 128.07, 128.16, 128.26,
128.36, 128.40, 129.64, 129.83, 132.31, 132.86, 135.63,
135.68, 136.37, 136.94, 137.01, 137.20, 137.26, 137.40,
137.99, 138.21, 138.49, 138.58; MALDI-TOF MS:
[M+Na]+ calcd for C132H139F5N18O25SiNa 2521.97, found
2523.00; HRMS ESI-TOF: [M+Na]+ calcd for
C132H139F5N18O25SiNa 2521.9746, found 2521.9718.
H-4Bac, H-3Bac, 2H), 3.15 (dd, J¼5.6, 8.8 Hz, H-6aGalNIII
,
1H), 3.21 (dd, J¼5.2, 9.2 Hz, H-6aGalNII, 1H), 3.31 (dd,
J¼8.0, 9.8 Hz, H-2Bac, 1H), 3.48–3.56 (m, H-6bGalNIII, H-
6aGalNI, H-2Glc, H-6aGlc, H-6bGlc, 5H), 3.58–3.67 (m, H-
2
GalNI, H-2GalNII, H-2GalNIII, H-3Glc, 4H), 3.70 (br t,
J¼9.6 Hz, H-6bGalNII, 1H), 3.81–3.87 (m, H-3GalNI, H-4Glc
,
H-6bGalNI, H-5Glc, 4H), 3.93 (d, J¼12.0 Hz, PhCH2, 1H),
4.03 (d, J¼12.0 Hz, PhCH2, 1H), 4.07–4.10 (m, H-3GalNIII
,
H-3GalNII,2H),4.16(m,H-5GalNI,1H),4.27–4.29(m,H-5GalNII
,
H-4GalNIII, 2H), 4.31 (d, J¼7.6 Hz, H-1Bac, 1H), 4.33–4.35
(m, H-5GalNIII, H-4GalNII, H-4GalNI, 3H), 4.43–4.55 (m,
PhCH2, 8H), 4.64 (d, J¼7.2 Hz, H-1Glc, 1H), 4.72–4.79 (m,
PhCH2, 4H), 4.85–4.89 (m, PhCH2, 3H), 5.04–5.08 (m, H-
1
GalNII, H-1GalNIII, PhCH2, 3H), 5.23 (d, J¼3.6 Hz, H-1GalNI
,
1H), 7.11–7.62 (m, Ar, 51H), 7.64–7.67 (m, Ar, 4H); 13C
NMR (CDCl3, 100 MHz): d 17.95, 19.25, 26.94, 59.31,
59.71, 59.82, 66.51, 66.67, 67.55, 67.77, 68.22, 68.70,
69.08, 69.54, 70.97, 71.64, 71.74, 71.85, 73.03, 73.22,
4.32. tert-Butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-
deoxy-a-D-galactopyranosyl-(1/4)-[2,3,4,6-tetra-O-
benzyl-b-D-glucopyranosyl-(1/3)]-2-azido-6-O-