Sulfide-Mediated DehydratiVe Glycosylation
J. Am. Chem. Soc., Vol. 123, No. 36, 2001 8771
1
C6D6) δ 139.9, 139.6, 139.4, 138.8, 137.9, 128.6, 128.5, 128.4, 128.3,
128.2, 128.1, 127.9, 127.7, 127.6, 127.5, 127.4, 109.2, 102.7, 96.8,
82.9, 80.4, 79.3, 78.9, 76.6, 75.3, 75.2, 74.9, 73.9, 73.5, 73.3, 69.2,
69.1, 64.9, 28.1, 26.3, 18.4; FTIR (neat film) 2907, 2853, 2360, 2334,
1454, 1143, 1085, 1068, 1026, 735, 697 cm-1; HRMS (FAB) m/z:
Calcd for C50H56O10Na (M + Na) 839.3775, found 839.3771.
Methyl O-3,4,6-tri-O-benzyl-2-O-benzoyl-â-D-glucopyranosyl-
benzene); [R]24 ) +10.4° (c ) 1.4, CHCl3); H NMR (500 MHz,
D
C6D6) δ 7.43-7.33 (m, 4H, ArH), 7.31-7.23 (m, 9H, ArH), 7.17-
7.06 (m, 22H, ArH), 5.07 (d, 1H, J ) 11.5 Hz, OBn), 5.04 (d, 1H, J
) 11.5 Hz, OBn), 5.01 (d, 1H, J ) 11.2 Hz, OBn), 4.90 (d, 1H, J )
11.7 Hz, OBn), 4.78 (d, 1H, J ) 11.2 Hz, OBn), 4.77 (d, 1H, J ) 11.2
Hz, OBn), 4.68 (d, 1H, J ) 3.4 Hz, H-1′), 4.66 (d, 1H, J ) 10.3 Hz,
OBn), 4.61 (d, 1H, J ) 11.2 Hz, OBn), 4.60 (d, 1H, J ) 12.2 Hz,
OBn), 4.51 (t, 2H, J ) 12.2 Hz, OBn), 4.46 (d, 1H, J ) 11.9 Hz,
OBn), 4.44 (d, 1H, J ) 7.6 Hz, H-1), 4.37 (dd, 1H, J ) 10.7, 1.7 Hz,
H-6′), 4.31-4.23 (m, 3H, H-5, OBn), 4.14 (dd, 1H, J ) 9.8, 7.6 Hz,
H-2), 4.04 (ddd, H, J ) 10.0, 4.9, 1.5 Hz, H-5′), 3.84-3.81 (m, 2H,
H-4, H-6′), 3.78-3.73 (m, 2H, H-6, H-4′), 3.64-3.60 (m, 2H, H-6,
H-2′), 3.41 (t, 1H, J ) 6.6 Hz, H-3′), 3.37 (dd, 1H, J ) 9.8, 2.9 Hz,
H-3), 3,12 (s, 3H, OMe); 13C NMR (126 MHz, C6D6) δ 139.8, 139.7,
139.6, 139.2, 139.1, 138.8, 128.6, 128.5, 128.49, 128.46, 128.42, 128.4,
128.3, 128.1, 128.0, 127.9, 127.7, 127.6, 127.5, 127.4, 104.7, 98.2,
82.7, 82.3, 81.1, 79.9, 76.6, 75.5, 75.3, 75.2, 74.8, 74.6, 73.7, 73.5,
72.9, 72.7, 70.7, 69.0, 68.7, 54.9; FTIR (neat film) 3030, 2921, 2870,
1496, 1454, 1361, 1093, 1068, 1028, 735, 697 cm-1; HRMS (FAB)
m/z: Calcd for C62H66O11Na (M + Na) 1009.4505, found 1009.4503.
Anal. Calcd for C62H66O11: C, 75.43; H, 6.74. Found: C, 75.16; H,
6.73.
(1f6)-2,3,4-tri-O-benzyl-r-D-glucopyranoside (19): Rf ) 0.35 (9%
1
acetonitrile in benzene); [R]25 ) +20° (c ) 1.8, CHCl3); H NMR
D
(500 MHz, C6D6) δ 8.09-8.07 (m, 2H, ArH), 7.30-6.91 (m, 33H,
ArH), 5.75 (dd, 1H, J ) 9.5, 7.8 Hz, H-2), 4.90 (d, 1H, J ) 11.5 Hz,
OBn), 4.69-4.65 (m, 5H, OBn), 4.50 (d, 1H, J ) 3.4 Hz, H-1′), 4.48
(d, 1H, J ) 7.8 Hz, H-1), 4.46-4.38 (m, 5H, OBn), 4.30 (d, 1H, J )
11.9 Hz, OBn), 4.25 (dd, 1H, J ) 10.5, 1.7 Hz, H-6′), 4.14 (t, 1H, J )
9.3 Hz, H-3′), 3.87 (ddd, 1H, J ) 10.3, 4.4, 1.5 Hz, H-5), 3.77 (t, 1H,
J ) 9.3 Hz, H-3), 3.71-3.61 (m, 5H, H-4, H-5, H-6, H-4′, H-6′), 3.47-
3.43 (m, 2H, H-6, H-2′), 3.04 (s, 3H, OMe); 13C NMR (126 MHz,
C6D6) δ 165.2, 139.8, 139.5, 139.3, 139.0, 138.9, 138.7, 132.9, 130.9,
130.1, 128.6, 128.56, 128.50, 128.4, 128.35, 128.3, 128.2, 128.1, 127.9,
127.8, 127.7, 127.68, 127.67, 127.6, 127.5, 127.4, 127.3, 101.8, 98.1,
82.9, 82.1, 81.1, 78.5, 78.1, 75.9, 75.3, 74.9, 74.8, 74.6, 74.3, 73.5,
72.8, 70.3, 69.1, 68.5, 54.8; FTIR (neat film) 3030, 2925, 1729, 1453,
1267, 1093, 1065, 1028, 736, 697 cm-1; HRMS (FAB) m/z: Calcd for
C62H64O12Na (M + Na) 1023.4291, found 1023.4295. Anal. Calcd for
C62H64O12: C, 74.38; H, 6.44. Found: C, 74.25; H, 6.48.
Benzyl O-2,3,4,6-tetra-O-benzyl-D-glucopyranosyl-(1f4)-2,3-di-
O-isopropylidene-r-L-rhamnopyranoside (22): R: Rf ) 0.41 (9%
acetonitrile in benzene); [R]24 ) +24.2° (c ) 0.9, CHCl3); H NMR
1
D
(500 MHz, C6D6) δ 7.36-7.17 (m, 8H, ArH), 7.16-7.06 (m, 17H,
ArH), 5.14 (s, 1H, H-1′), 5.05 (d, 1H, J ) 11.0 Hz, OBn), 5.04 (d, 1H,
J ) 3.4 Hz, H-1), 5.01 (d, 1H, J ) 11.5 Hz, OBn), 4.92 (d, 1H, J )
11.5 Hz, OBn), 4.81 (d, 1H, J ) 11.5 Hz, OBn), 4.59 (d, 1H, J ) 11.4
Hz, OBn), 4.54-4.47 (m, 3H, H-2′, OBn), 4.45 (d, 1H, J ) 11.5 Hz,
OBn), 4.39-4.37 (m, 1H, H-5), 4.30 (t, 1H, J ) 9.5 Hz, H-3), 4.21-
4.16 (m, 3H, H-3′, OBn), 4.10 (dd, 1H, J ) 10.0, 9.3 Hz, H-4), 4.01
(dd, 1H, J ) 11.0, 2.7 Hz, H-6), 3.89 (dq, 1H, J ) 10.0, 6.1 Hz, H-5′),
3.85 (dd, 1H, J ) 11.0, 1.9 Hz, H-6), 3.58-3.55 (m, 2H, H-2, H-4′),
1.53 (s, 3H), 1.40 (d, 3H, J ) 6.3 Hz), 1.18 (s, 3H); 13C NMR (126
MHz, C6D6) δ 139.8, 139.6, 139.3, 138.8, 137.8, 128.6, 128.4, 128.3,
128.1, 127.9, 127.8, 127.6, 127.5, 127.4, 109.0, 99.0, 96.7, 82.6, 82.4,
81.2, 78.6, 77.6, 76.7, 75.5, 75.1, 74.1, 73.5, 71.6, 69.1, 68.9, 65.6,
28.4, 26.5, 17.6; FTIR (neat film) 3030, 2933, 2866, 1454, 1139, 1083,
1044, 1027, 735, 697 cm-1; HRMS (FAB) m/z: Calcd for C50H56O10-
Methyl O-3,4,6-tri-O-benzyl-2-O-benzoyl-â-D-glucopyranosyl-
(1f4)-2,3,6-tri-O-benzyl-r-D-glucopyranoside (20). Rf ) 0.28 (9%
1
acetonitrile in benzene); [R]25 ) +22.4° (c ) 2.4, CHCl3); H NMR
D
(500 MHz, C6D6) δ 8.09-8.07 (m, 2H, ArH), 7.49-6.97 (m, 33H,
ArH), 5.76 (dd, 1H, J ) 9.5, 8.1 Hz, H-2), 5.30 (d, 1H, J ) 11.9 Hz,
OBn), 5.07 (d, 1H, J ) 8.1 Hz, H-1), 4.94 (d, 1H, J ) 11.9 Hz, OBn),
4.72 (d, 1H, J ) 11.5 Hz, OBn), 4.71 (d, 1H, J ) 11.2 Hz, OBn), 4.64
(d, 1H, J ) 11.2 Hz, OBn), 4.57 (d, 1H, J ) 12.5 Hz, OBn), 4.55 (d,
1H, J ) 3.2 Hz, H-1′), 4.55-4.48 (m, 2H, OBn), 4.43-4.36 (m, 3H,
OBn), 4.32-4.28 (m, 2H, H-4′, OBn), 4.23 (t, 1H, J ) 9.3 Hz, H-3′),
3.93 (dd, 1H, J ) 11.0, 3.7 Hz, H-6′), 3.78-3.69 (m, 4H, H-3, H-4,
H-6, H-5′), 3.59-3.55 (m, 2H, H-5, H-6), 3.53 (dd, 1H, J ) 11.0, 1.5
Hz, H-6′), 3.49 (dd, 1H, J ) 9.3, 3.7 Hz, H-2′), 2.94 (s, 3H, OMe);
13C NMR (126 MHz, C6D6) δ 164.9, 140.6, 139.3, 139.2, 139.03, 139.0,
138.7, 133.0, 130.7, 130.0, 128.7, 128.6, 128.5, 128.4, 128.3, 128.1,
127.93, 127.9, 127.7, 127.6, 127.54, 127.5, 127.1, 101.1, 98.4, 83.5,
80.5, 80.4, 78.5, 77.7, 76.1, 75.2, 75.0, 74.9, 74.8, 73.7, 73.6, 73.1,
70.7, 69.1, 68.7, 54.8; FTIR (neat film) 3030, 2901, 2860, 1731, 1496,
1453, 1362, 1266, 1096, 1070, 1048, 1027, 736, 698 cm-1; HRMS
(FAB) m/z: Calcd for C62H64O12Na (M + Na) 1023.4291, found
1023.4295. Anal. Calcd for C62H64O12: C, 74.30; H, 6.44. Found: C,
74.17; H, 6.45.
Na (M + Na) 839.3775, found 839.3771. â: Rf ) 0.50 (9% acetonitrile
1
in benzene); [R]24 ) -15.3° (c ) 0.5, CHCl3); H NMR (500 MHz,
D
C6D6) δ 7.41-7.21 (m, 6H, ArH), 7.19-7.07 (m, 19H, ArH), 5.23 (d,
1H, J ) 7.8 Hz, H-1), 5.19 (s, 1H, H-1′), 5.0 (d, 1H, J ) 11.2 Hz,
OBn), 4.96 (d, 1H, J ) 11.2 Hz, OBn), 4.87 (d, 1H, J ) 11.5 Hz,
OBn), 4.76 (d, 1H, J ) 11.5 Hz, OBn), 4.73 (d, 1H, J ) 11.5 Hz,
OBn), 4.57 (d, 2H, J ) 11.4 Hz, OBn), 4.46 (d, 1H, J ) 12.4 Hz,
OBn), 4.41-4.38 (m, 2H, H-3′, OBn), 4.26 (d, 1H, J ) 11.9 Hz, OBn),
4.21 (d, 1H, J ) 5.6 Hz, H-2′), 4.10 (dd, 1H, J ) 9.8, 7.3 Hz, H-4′),
3.93 (dq, 1H, J ) 10.0, 6.1 Hz, H-5′), 3.76-3.66 (m, 4H, H-3, H-4,
H-6), 3.57 (t, 1H, J ) 8.3 Hz, H-2), 3.50-3.48 (m, 1H, H-5), 1.58 (d,
3H, J ) 6.3 Hz), 1.50 (s, 3H), 1.22 (s, 3H); 13C NMR (126 MHz,
C6D6) δ 139.6, 139.5, 139.3, 139.0, 137.9, 128.6, 128.5, 128.4, 128.3,
128.1, 127.9, 127.6, 127.59, 127.5, 127.4, 109.4, 102.2, 96.9, 85.2,
83.0, 78.84, 78.8, 78.3, 76.7, 75.5, 74.9, 74.7, 73.4, 69.2, 69.1, 64.9,
28.1, 26.4, 18.2; FTIR (neat film) 2905, 2860, 1453, 1082, 1065, 1027,-
735, 697 cm-1; HRMS (FAB) m/z: Calcd for C50H56O10Na (M + Na)
839.3775, found 839.3771.
Methyl O-2,3,4,6-tetra-O-benzyl-â-D-galactopyranosyl-(1f6)-
2,3,4-tri-O-benzyl-r-D-glucopyranoside (21). R: Rf ) 0.49 (5%
1
acetonitrile in benzene); [R]24 ) +41.1° (c ) 2.4, CHCl3); H NMR
D
(500 MHz, C6D6) δ 7.40-7.32 (m, 10H, ArH), 7.27-7.24 (m, 4H,
ArH), 7.18-7.04 (m, 21H, ArH), 5.28 (d, 1H, J ) 3.7 Hz, H-1), 5.10
(d, 1H, J ) 11.2 Hz, OBn), 5.05 (d, 1H, J ) 11.5 Hz, OBn), 5.01 (d,
1H, J ) 11.2 Hz, OBn), 4.82 (d, 1H, J ) 11.0 Hz, OBn), 4.80 (d, 1H,
J ) 11.2 Hz, OBn), 4.71 (d, 1H, J ) 12.2 Hz, OBn), 4.63 (d, 1H, J )
11.2 Hz, OBn), 4.60 (d, 1H, J ) 3.4 Hz, H-1′), 4.58 (d, 1H, J ) 11.9
Hz, OBn), 4.55 (s, 2H, OBn), 4.49 (d, 1H, J ) 12.2 Hz, OBn), 4.37
(d, 1H, J ) 11.9 Hz, OBn), 4.34 (d, 1H, J ) 11.9 Hz, OBn), 4.29-
4.27 (m, 2H, H-2, OBn), 4.26-4.20 (m, 2H, H-5, H-3′), 4.10 (dd, 1H,
J ) 10.0, 2.7 Hz, H-3), 4.01 (dd, 1H, J ) 11.9, 3.7 Hz, H-6′), 3.98 (d,
1H, J ) 1.7 Hz, H-4), 3.94-3.87 (m, 2H, H-4′, H-5′), 3.86-3.80 (m,
2H, H-6,H-6′), 3.73 (dd, 1H, J ) 9.0, 5.9 Hz, H-6), 3.49 (dd, 1H, J )
9.5, 3.4 Hz, H-2′), 3.11 (s, 3H, OMe); 13C NMR (126 MHz, C6D6) δ
139.8, 139.7, 130.6, 139.59, 139.5, 139.3, 138.9, 128.6, 128.5, 128.49,
128.4, 128.3, 128.2, 128.1, 127.9, 127.8, 127.7, 127.6, 127.58, 127.5,
127.4, 98.4, 98.3, 82.4, 81.2, 78.6, 78.3, 77.7, 76.2, 75.5, 75.3, 75.0,
73.5, 73.0, 72.9, 72.7, 71.3, 70.1, 69.5, 66.3, 54.9; FTIR (neat film)
3030, 2914, 2866, 1496, 1453, 1160, 1134, 1099, 1056, 1028, 736,
697 cm-1; HRMS (FAB) m/z: Calcd for C62H66O11Na (M + Na)
1009.4505, found 1009.4503. Anal. Calcd for C62H66O11: C, 75.43;
H, 6.74. Found: C, 75.11; H, 6.73. â: Rf ) 0.42 (5% acetonitrile in
Benzyl O-3-O-acetyl-2,3-di-O-isopropylidene-r-L-rhamnopyra-
nosyl-(1f4)-2,3-di-O-isopropylidene-r-L-rhamnopyranoside (23): Rf
) 0.38 (9% acetonitrile in benzene); [R]24D ) -41.3° (c ) 3.0, CHCl3);
1H NMR (500 MHz, CDCl3) δ 7.38-7.31 (m, 5H, ArH), 5.63 (s, 1H,
H-1), 5.06 (s, 1H, H-1′), 4.88 (dd, 1H, J ) 10.0, 7.8 Hz, H-4), 4.70 (d,
1H, J ) 11.7 Hz, OBn), 4.52 (d, 1H, J ) 11.7 Hz, OBn), 4.23 (dd,
1H, J ) 7.1, 5.6 Hz, H-3′), 4.16-4.14 (m, 2H, H-2, H-2′), 4.11 (dd,
1H, J ) 7.8, 5.1 Hz, H-3), 3.73 (dq, 2H, J ) 10.0, 6.1 Hz, H-5, H-5′),
3.59 (dd, 1H, J ) 9.8, 7.3 Hz, H-4′), 2.10 (s, 3H), 1.56 (s, 3H), 1.54
(s, 3H), 1.35 (s, 3H), 1.32 (s, 3H), 1.26 (d, 3H, J ) 6.1 Hz), 1.15 (d,
3H, J ) 6.3 Hz); 13C NMR (126 MHz, CDCl3) δ 170.0, 136.9, 128.5,
128.2, 127.9, 109.6, 109.5, 96.1, 95.5, 78.5, 76.7, 76.2, 76.1, 75.5, 74.2,
69.1, 64.3, 64.0, 27.9, 27.6, 26.4, 26.3, 21.0, 17.8, 16.7; FTIR (neat