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Helvetica Chimica Acta ± Vol. 82 (1999)
(d, C(1I )); 76.48 (d, C(4I )); 72.89 (d, C(3II )); 72.66 (d, C(5I )); 72.44 (d, C(3I )); 71.90 (d, C(5II )); 71.56
(d, C(2I )); 71.37 (d, C(2II )); 70.07 (t, ArCH2CH2); 67.71 (d, C(4II )); 61.86 (t, C(6I )); 61.47 (t, C(6II )); 32.86
(t, ArCH2); 20.75, 20.52 (2q, 2 Me); 20.41 (q, 5 Me). CI-MS: 809 (33), 808 (70, [M NH4] ), 790 (6, M ), 619
(7), 331 (42), 169 (43), 154 (100). Anal. calc. for C38H46O18 (790.77): C 57.72, H 5.86; found: C 57.64, H 5.91.
2-(Naphthalen-1-yl)ethyl 2,3,4,6-Tetra-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopy-
ranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopyranoside (34). A suspension of 12 (52 mg, 0.30 mmol), 17 [43]
(377 mg, 0.37 mmol), basic zinc carbonate (200 mg, 0.36 mmol), and 3- molecular sieves (150 mg) in dry 1,2-
dichloroethane (15 ml) was stirred at 1108 for 20 h. Filtration, evaporation, and FC (hexane/AcOEt 1 : 1) gave
34 (220 mg, 67%). Solid. Rf (hexane/AcOEt 4 : 6) 0.37. M.p. 2018. [a]D25
24.0 (c 0.93, CHCl3). IR (CHCl3):
3015w, 2975w, 2866w, 1755s, 1368m, 1236s, 1165w, 1048m, 905w, 877w. 1H-NMR (300 MHz, CDCl3): 7.98
(dd, J 1.4, 7.8), 7.85 (dd, J 1.8, 7.5), 7.73 (br. d, J 8.1), 7.51 (dt, J 1.8, 6.8), 7.47 (dt, J 1.2, 6.8), 7.38
(dd, J 7.2, 8.1), 7.32 (dd, J 1.3, 6.9) (7 arom. H); 5.12 (t, J 9.2), 5.11 (t, J 9.3, 2H) (H C(3I ), H C(3II ),
H
C(3III )); 5.04 (t, J 9.3, H C(4III )); 4.89 (dd, J 7.8, 9.6), 4.88 (dd, J 8.0, 9.6) (H C(2I ), H C(2III ));
4.83 (dd, J 7.8, 9.3, H C(2II )); 4.51 (dd, J 2.2, 12.5, H C(6I )); 4.46 (d, J 7.9, H C(1II ); H C(1III )); 4.44
(d, J 8.1, H C(1I )); 4.39 (dd, J 1.9, 12.2, H C(6II )); 4.34 (dd, J 4.4, 12.8, H C(6III )); 4.20 (ddd, J 5.9,
7.4, 9.6, ArCH2CH); 4.10 (dd, J 5.0, 11.8, H' C(6II )); 4.06 (dd, J 4.6, 12.2, H' C(6I )); 4.03 (dd, J 2.2, 12.4,
H' C(6III )); 3.79 (td, J ꢁ 7.5, 9.6, ArCH2CH); 3.75 (dd, J 9.1, 9.6, H C(4I )); 3.74 (t, J 9.5, H C(4II )); 3.62
(ddd, J 2.2, 4.1, 9.7, H C(5III )); 3.60 ± 5.51 (m, H C(5I ), H C(5II )); 3.425 ± 3.26 (AB of ABMX, ArCH2);
2.14, 2.09, 2.08, 2.02, 2.01, 2.00, 1.98, 1.97, 1.95, 1.82 (10s, 10 Ac). 13C-NMR (75 MHz, CDCl3): 170.70, 170.51 (2s,
2 CO); 170.39 (s, 2 CO); 169.96 (s, 2 CO); 169.67 (s, CO); 169.50 (s, 2 CO); 169.28 (s, CO); 134.38
(s, C(1)); 133.93 (s, C(4a)); 132.14 (s, C(8a)); 128.93, 127.30, 127.12, 126.17 (4d, C(2), C(3), C(4), C(5));
125.66, 125.58 (2d, C(6), C(7)); 123.62 (d, C(8)); 100.86 (d, C(1III )); 100.60 (d, C(1II )); 100.52 (d, C(1I )); 76.52
(d, C(4I )); 76.18 (d, C(4II )); 72.92 (d, C(5I )); 72.74 (d, C(3II ), C(3III ), C(5II )); 72.44 (d, C(3I )); 72.05
(d, C(5III )); 71.81 (d, C(2II )); 71.60 (d, C(2I )); 71.54 (d, C(2III )); 70.09 (t, ArCH2CH2); 67.76 (d, C(4III ));
62.15 (t, C(6II )); 61.81 (t, C(6I )); 61.52 (t, C(6III )); 32.92 (t, ArCH2); 20.81, 20.67, 20.55 (3q, 3 Me); 20.46
(q, 7 Me). FAB-MS: 1101 (28, [M Na] ), 1079 (13, [M 1] ), 1078 (19, M ), 908 (13), 907 (30), 619 (100),
331 (39), 155 (73). Anal. calc. for C50H62O26 (1079.02): C 55.66, H 5.79; found: C 55.35, H 5.83.
2-(Naphthalen-1-yl)ethyl 2,3,4,6-Tetra-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopy-
ranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopyranoside (35).
A
suspension of 12 (52 mg, 0.30 mmol), 18 (510 mg, 0.40 mmol), basic zinc carbonate (80 mg, 0.15 mmol), and
3- molecular sieves (70 mg) in dry toluene (10 ml) was stirred at 1108 for 7 h. Filtration, evaporation, and FC
(hexane/AcOEt 3 : 7) gave 35 (300 mg, 73%). Solid. Rf (hexane/AcOEt 3 : 7) 0.50. M.p. 2168. [a]D25
23.0 (c
0.50, CHCl3). IR (CHCl3): 3028w, 2957w, 2874w, 1755s, 1429w, 1367m, 1232s, 1164w, 1129w, 1054m, 905w.
1H-NMR (500 MHz, CDCl3): 7.98 (d, J 8.3), 7.84 (dd, J 1.5, 7.9), 7.72 (d, J 8.1), 7.51 (dt, J 1.7, 6.9), 7.45
(dt, J 1.3, 6.7), 7.38 (dd, J 7.1, 8.1), 7.32 (br. d, J 6.0) (7 arom. H); 5.11 (t, J 9.3), 5.10 (t, J 9.3), 5.092
(t, J 9.2), 5.091 (t, J 9.2), 5.04 (t, J 9.6) (H C(3I±IV ), H C(4IV )); 4.89 (dd, J 7.9, 9.2), 4.88 (dd, J 7.9,
9.6), 4.816 (dd, J 7.8, 9.4), 4.813 (dd, J 7.9, 9.4) (H C(2I±IV )); 4.46 (d, J 7.9), 4.45 (d, J 7.8), 4.44 (d, J
7.9), 4.43 (d, J 7.9) (H C(1I±IV )); 4.49 (dd, J 2.1, 12.1), 4.390 (dd, J 2.0, 12.0), 4.389 (dd, J 2.5, 12.4)
(H C(6I±III )); 4.34 (dd, J 4.4, 12.5, H C(6IV )); 4.19 (ddd, J 5.7, 7.6, 9.6, ArCH2CH); 4.08 (dd, J 5.0, 12.0,
2 H), 4.06 (dd, J 5.1, 12.0) (H' C(6I±III )); 4.03 (dd, J 2.2, 12.5, H' C(6IV )); 3.79 (td, J 7.5, 9.7,
ArCH2CH); 3.78 (dd, J 8.7, 9.7), 3.73 (dd, J 9.0, 9.5, 2 H) (H C(4I±III )); 3.62 (ddd, J 2.3, 4.3, 9.9), 3.57
(ddd, J ꢁ 2.0, 5.0, 9.5), 3.56 (ddd, J ꢁ 2.0, 5.0, 9.5), 5.54 (ddd, J ꢁ 2.0, 5.0, 9.5) (H C(5I±IV )); 3.38 ± 3.28 (AB of
ABMX, ArCH2); 2.13, 2.12, 2.09, 2.03, 2.02 (5s, 5 Ac); 2.00 (s, 2 Ac); 1.99, 1.98, 1.97, 1.95, 1.94, 1.82 (6s, 6 Ac).
13C-NMR (75 MHz, CDCl3): 170.57, 170.41, (2s, 2 CO); 170.26 (s, 3 CO); 169.86 (s, CO); 169.81
(s, 2 CO); 169.52, 169.40, 169.37, 169.32, 169.16 (5s, 5 CO); 134.25 (s, C(1)); 133.80 (s, C(4a)); 131.97
(s, C(8a)); 128.80, 127.16, 127.00, 126.03 (4d, C(2), C(3), C(4), C(5)); 125.55, 125.47 (2d, C(6), C(7)); 123.51
(2d, C(8)); 100.75 (d, C(1IV )); 100.58, 100.49 (2d, C(1II ), C(1III )); 100.45 (d, C(I )); 76.41 (d, C(4I )); 76.09, 75.99
(2d, C(4II ), C(4III )); 72.76 (d, C(5I )); 72.64 (d, C(3IV )); 72.58 (d, C(5II ), C(5III )); 72.52 (2d), 72.26 (d)
(C(3I±III )); 71.90 (d, C(5IV )); 71.75, 71.61 (2d, C(2II ), C(2III )); 71.43 (d, C(2I )); 71.35 (d, C(2IV )); 69.96
(t, ArCH2CH2); 67.58 (d, C(4IV )); 61.97 (t, C(6II ), C(6III )); 61.71 (t, C(6I )); 61.35 (t, C(6IV )); 32.77 (t, ArCH2);
20.68 (q, Me); 20.58 (q, 2 Me); 20.45 (q, 5 Me); 20.33 (q, 5 Me). FAB-MS: 1499 (26), 1389 (59), 1368 (50), 1367
(73, [M 1] ), 1366 (100, M ), 1195 (67), 907 (60), 619 (79), 155 (34), 154 (44). Anal. calc. for C62H78O34
(1367.27): C 54.46, H 5.75; found: C 54.49, H 5.94.
2-(Naphthalen-1-yl)ethyl 2,3,4,6-Tetra-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopy-
ranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,-
3,6-tri-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-d-glucopyranosyl-(1 ! 4)-2,3,6-tri-O-acetyl-b-