9926
J3,4=9.8 Hz, H-3), 6.26 (d, 1H, J1,2=10.5 Hz, H-1), 7.25–7.61 (m, 10H, Ph, H-3ar), 7.82–7.92 (m, 6H, Ph), 8.25
(dd, 1H, J4ar,6ar=2.6 Hz, J4ar,3ar=8.8 Hz, H-4ar), 9.28 (d, 1H, H-6ar).
9. Lemieux, R. V. In Methods in Carbohydrate Chemistry; Whistler, R. L.; Wolfrom, M. L., Eds.; Academic Press:
New York, 1963; Vol. 2, p. 221.
10. Cerny´, M.; Paca´k, J. Collect. Czech. Chem. Commun. 1959, 24, 2566.
11. Ito, Y.; Ogawa, T. Tetrahedron Lett. 1987, 28, 4701.
1
12. All new compounds gave satisfactory H NMR (300 MHz) spectroscopic and elemental analytical data. Selected
data: 8: (5-Nitro-2-pyridyl) 2,3,4,6-tetra-O-acetyl-i-D-glucopiranosyl-(16)-2,3,4-tri-O-benzoyl-1-thio-i-D-glu-
1
copyranoside: syrup, [h]=97.8 (c 0.3, CHCl3), H NMR l 1.95, 1.97, 1.98, 2.01 (4s, 12H, 4×CH3CO), 3.52 (m,
1H, H-5%), 3.78 (dd, 1H, J6,5=6.3 Hz, J6,6a=11.5 Hz, H-6), 4.01 (dd, 1H, J6a,5=1.7 Hz, J6a,6=11.5 Hz, H-6a),
4.03 (dd, 1H, J6a%,5%=2.2 Hz, J6a%,6%=12.2 Hz, H-6a%), 4.17 (dd, 1H, J6%,5%=4.9 Hz, J6%,6a%=12.2 Hz, H-6%), 4.23 (m,
1H, H-5), 4.54 (d, 1H, J1%,2%=7.3 Hz, H-1%), 4.89–5.0 (m, 3H, H-2%, H-3%, H-4%), 5.49 (dd, 1H, J4,5=9.8 Hz,
J
4,3=9.8 Hz, H-4), 5.69 (dd, 1H, J2,3=9.8 Hz, J2,1=9.8 Hz, H-2), 6.02 (dd, 1H, J3,4=9.5 Hz, J3,2=9.8 Hz, H-3),
6.16 (d, 1H, J1,2=9.8 Hz, H-1), 7.25–7.57 (m, 9H, Ph, H-3ar), 7.79–7.94 (m, 7H, Ph, H-3ar), 8.31 (dd, 1H,
4ar,6ar=2.6 Hz, J4ar,3ar=8.8 Hz, H-4ar), 9.31 (d, 1H, H-6ar). 9: (5-Nitro-2-pyridyl) 2,3,4,6-tetra-O-benzyl- -glu-
-glucopyranoside: syrup, H NMR (a anomer) l 3.44–3.51 (m,
J
D
1
copiranosyl-(16)-2,3,4-tri-O-benzoyl-1-thio-i-
D
4H, H-2%, H-5%, H-6, H-6%), 3.64 (dd, 1H, J6a,5=2.4 Hz, J6a,6=11.2 Hz, H-6a), 3.66–3.75 (m, 2H, H-5, H-6a%), 3.86
(dd, 1H, J4%,5%=8.1 Hz, J4%,3%=8.2 Hz, H-4%), 4.33 (dd, 1H, J3%,2%=8.2 Hz, J3%,4%=8.2 Hz, H-3%), 4.25, 4.52 (AB, 2H,
J=10.5 Hz, CH2Ph), 4.41, 4.60 (AB, 2H, J=12.0 Hz, CH2Ph), 4.61, 4.76 (AB, 2H, J=12.2 Hz, CH2Ph), 4.70,
4.93 (AB, 2H, J=10.7 Hz, CH2Ph), 4.65 (d, 1H, J1%,2%=3.7 Hz, H-1%), 5.51 (dd, 1H, J4,5=9.8 Hz, J4,3=9.3 Hz,
H-4), 5.67 (dd, 1H, J2,3=9.5 Hz, J2,1=10.5 Hz, H-2), 6.03 (dd, 1H, J3,4=9.3 Hz, J3,2=9.5 Hz, H-3), 6.04 (d, 1H,
J1,2=10.5 Hz, H-1), 6.87–6.90 (m, 2H, Ph), 6.99 (d, 1H, J3ar,4ar=8.8 Hz, H-3ar), 7.18–7.39 (m, 28H, Ph),
7.79–7.97 (m, 6H, Ph, H-4ar), 9.17 (d, 1H, J6ar,4ar=2.4 Hz, H-6ar). (b anomer) l 3.31–3.39 (m, 2H, H-2%, H-5%),
3.45–3.60 (m, 5H, H-5, H-6, H-6%, H-6a, H-6a%), 3.82 (dd, 1H, J4%,5%=8.2 Hz, J4%,3%=8.1 Hz, H-4%), 4.15 (d, 1H,
J1%,2%=10.9 Hz, H-1%), 4.26, 4.42 (AB, 2H, J=10.5 Hz, CH2Ph), 4.36, 4.47 (AB, 2H, J=12.2 Hz, CH2Ph), 4.38
(dd, 1H, J3%,4%=8.1 Hz, J3%,2%=8.1 Hz, H-3%), 4.62, 4.77 (AB, 2H, J=10.7 Hz, CH2Ph), 4.64, 4.75 (AB, 2H, J=10.7
Hz, CH2Ph), 5.51 (dd, 1H, J4,5=9.8 Hz, J4,3=9.4 Hz, H-4), 5.73 (dd, 1H, J2,3=9.4 Hz, J2,1=10.5 Hz, H-2), 6.07
(dd, 1H, J3,4=9.4 Hz, J3,2=9.4 Hz, H-3), 6.23 (d, 1H, J1,2=10.5 Hz, H-1), 6.91–7.01 (m, 3H, Ph), 7.10–7.45 (m,
25H, Ph, H-3ar), 7.79–7.95 (m, 9H, Ph, H-4ar), 9.04 (d, 1H, J6ar,4ar=2.4 Hz, H-6ar). 10: (5-Nitro-2-pyridyl)
2-deoxy-3,4-di-O-benzyl-
NMR l 1.09 (d, J=6.2 Hz, CH3(H-6%b)), 1.15 (d, J=6.0 Hz, CH3(H-6%a)), 1.39 (m, H-2%axb), 1.56 (ddd,
2%ax,2%eq=12.9 Hz, J2%ax,3%=10.0 Hz, H-2%axa), 2.04 (m, H-2%eqb), 2.29 (ddd, J2%eq,3%=4.9 Hz, H-2%eqa), 2.99 (dd,
L-rhamnopyranosyl-(16)-2,3,4-tri-O-benzoyl-1-thio-i-D
-glucopyranoside: syrup, 1H
J
J4%,5%=9.0 Hz, H-4%b), 3.07 (dd, J4%,5%=9.2 Hz, J4%,3%=4.6 Hz, H-4%a), 3.19 (dd, J6,5=6.4 Hz, J6,6a=9.5 Hz, H-6b),
3.43–3.54 (m, H-5%b, H-6ab), 3.61 (dd, J6,6a=12.0 Hz, J6,5=5.6 Hz, H-6a), 3.70 (dq, J5%,4%=9.3 Hz, H-5%a), 3.80
(dd, J6a,5=2.4 Hz, J6a,6=12.0 Hz, H-6aa), 3.88 (ddd, J3%,4%=4.6 Hz, H-3%a), 4.01 (m, H-3%b), 4.13 (m, H-5b), 4.15
(ddd, J5,6a=2.4 Hz, J5,6=5.6 Hz, J5,4=10.0 Hz, H-5a), 4.34 (dd, J1%2%eq=0.8 Hz, J1%2%ax=8.3 Hz, H-1%b), 4.43, 4.50
(AB, J=12.0 Hz, CH2Phb), 4.55, 4.59 (AB, J=11.4 Hz, CH2Pha), 4.57, 4.88 (AB, J=10.7 Hz, CH2Phb), 6.63,
4.94 (AB, J=11.4 Hz, CH2Pha), 4.75 (d, J1%,2%ax=2.9 Hz, H-1%a), 5.65 (dd, J4,5=10.0 Hz, J4,3=9.5 Hz, H-4a),
5.66 (dd, J4,5=10.0 Hz, J4,3=9.3 Hz, H-4b), 5.72 (dd, J2,3=9.9 Hz, J2,1=10.6 Hz, H-2b), 5.74 (dd, J2,3=9.5 Hz,
J2,1=10.5 Hz, H-2a), 6.02 (dd, J3,4=9.3 Hz, J3,2=9.9 Hz, H-3b), 6.03 (dd, J3,4=9.5 Hz, J3,2=9.5 Hz, H-3a), 6.18
(d, J1,2=10.5 Hz, H-1a), 6.22 (d, J1,2=10.6 Hz, H-1b), 7.32–7.95 (m, Ph, H-3ara, H-3arb), 7.81–7.95 (m, Ph), 8.19
(dd, J4ar,3ar=8.7 Hz, J4ar,6ar=2.4 Hz, H-4arb), 8.20 (dd, J4ar,6ar=2.4 Hz, J4ar,3ar=8.7 Hz, H-4ara), 9.28 (d,
J
4ar,6ar=2.7 Hz, H-6arb), 9.32 (d, H-6ara). 11: (5-Nitro-2-pyridyl) 2-deoxy-3,4,6-tri-O-benzyl-
D
-galactopyranosyl-
1
(16)-2,3,4-tri-O-benzoyl-1-thio-i-
D
-glucopyranoside: syrup, H NMR l 1.86 (ddd, 1H, J2%eq,1%:0 Hz, J2%eq,3%
=
4.6 Hz, J2%eq,2%ax=12.4 Hz, H-2e%q), 2.12 (ddd, 1H, J2%ax,3%=12.0 Hz, J2%ax,2%eq=12.4 Hz, J2%ax,1%=3.4 Hz, H-2a%x),
3.34–3.36 (m, 2H, H-6, H-5%), 3.66 (dd, 1H, J6a,5=3.1 Hz, J6a,6=11.3 Hz, H-6a), 3.70–3.89 (m, 4H, H-4%, H-5,
H-6%, H-6a%), 4.17 (m, 1H, H-3%), 4.20, 4.26 (AB, 2H, J=11.9 Hz, CH2Ph), 4.51 (s, 2H, CH2Ph), 4.53, 4.86 (AB,
2H, J=11.5 Hz, CH2Ph), 4.96 (d, 1H, J1%,2%ax=3.4 Hz, H-1%), 5.74 (dd, 1H, J2,3=9.8 Hz, J2,1=10.4 Hz, H-2), 5.75
(dd, 1H, J4,5=10.4 Hz, J4,3=9.5 Hz, H-4), 6.03 (dd, 1H, J3,4=9.5 Hz, J3,2=9.8 Hz, H-3), 6.20 (d, 1H, J1,2=10.4
Hz, H-1), 7.14–7.38 (m, 25H, Ph, H-3ar), 7.82–7.85 (m, 6H, Ph), 8.10 (dd, 1H, J4ar,3ar=8.7 Hz, J4ar,6ar=2.4 Hz,
H-4ar), 9.23 (d, 1H, J6ar,4ar=2.4 Hz, H-6ar).
13. Wandzik, I.; Szeja, W. Pol. J. Chem. 1998, 72, 703.
.