Glycosylation with Diphenyl Sulfonium Reagents
J. Am. Chem. Soc., Vol. 122, No. 18, 2000 4277
124.65, 122.29, 96.84, 78.56, 72.18, 71.26, 70.06, 68.27, 63.58, 57.16,
57.09, 54.93, 45.42, 43.28, 40.81, 40.27, 37.33, 37.01, 36.58, 36.47,
36.07, 36.04, 32.78, 29.32, 29.03, 28.75, 28.14, 24.94, 24.69, 23.39,
23.14, 21.92, 19.38, 12.79, 12.72; FTIR (neat film) 2934, 2866, 1730,
1452, 1267, 1108, 1070, 710 cm-1; HRMS (FAB) m/z calcd for
C61H75O10 (MH+) 967.5360, found 967.5373. Anal. Calcd for
C61H74O10: C, 75.75; H, 7.71. Found: C, 75.56; H, 7.67.
Methyl-O-(2,3,4,6-Tetra-O-benzyl-D-glucopyranosyl)-(1 f 4)-
2,3,6-tri-O-benzyl-r-D-glucopyranoside (17). R-Anomer: viscous oil;
Rf ) 0.67 (3% ethyl acetate in dichloromethane); [R]20D ) +40° (c )
1
1.1, CHCl3) (lit. [R]23 ) +47.5°, c ) 0.71, CHCl3); H NMR (500
D
MHz, CDCl3) δ 7.32-7.06 (m, 35 H), 5.70 (d, 1 H, J ) 3.6 Hz, H 1),
5.04 (d, 1 H, J ) 11.5 Hz), 4.88 (d, 1 H, J ) 10.84 Hz), 4.80 (d, 1 H,
J ) 11.7 Hz), 4.78 (d, J ) 10.6 Hz), 4.77 (d, 1 H, J ) 10.9 Hz), 4.70
(d, 1 H, J ) 12.17 Hz), 4.60 (d, 1 H, J ) 3.57 Hz, H 1′), 4.59 (d, 1 H,
J ) 11.9 Hz), 4.57 (d, 1 H, J ) 12.2 Hz), 4.54 (d, 1 H, J ) 11.9 Hz),
4.52 (d, 1 H, J ) 12.2 Hz), 4.49 (s, 2H), 4.41 (d, 1 H, J ) 10.86 Hz),
4.27 (d, 1 H, J ) 12.1 Hz), 4.09 (t, 1 H, J ) 8.8 Hz), 4.07 (t, 1 H, J
) 9.0 Hz), 3.90 (dd, 1 H, J ) 9.8, 8.6 Hz), 3.84 (m, 2H), 3.67 (m,
3H), 3.59 (dd, 1 H, J ) 9.2, 3.7 Hz), 3.49 (dd, 1 H, J ) 9.7, 3.6 Hz),
3.48 (dd, 1 H, J ) 10.7, 2.9 Hz), 3.38 (dd, 1 H, J ) 10.66, 1.56 Hz),
3.37 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 138.9, 138.8, 138.5, 138.2,
138.0, 138.0, 128.5, 128.4, 128.3, 128.3, 128.3, 128.1, 128.0, 127.9,
127.9, 127.7, 127.7, 127.6, 127.5, 127.4, 127.3, 127.1, 126.8, 110.0,
97.8, 96.7, 82.1, 82.1, 80.2, 79.5, 77.8, 76.8, 75.0, 74.4, 73.5, 73.4,
73.3, 73.2, 72.3, 71.0, 69.5, 69.0, 68.2, 55.2; FTIR (neat film) 3028,
2926, 1453, 1156, 1095, 1028, 734 cm-1; HRMS (FAB) m/z calcd for
C62H65O11 (M - H) 985.4527, found 985.4531. â-Anomer: white solid;
mp 88-89 °C (lit. mp 87-88 °C); Rf ) 0.56 (3% ethyl acetate in
Methyl-O-(2,3,4,6-Tetra-O-benzyl-D-glucopyranosyl)-(1 f 6)-
2,3,4-tri-O-benzyl-D-glucopyranoside (15).31 R-Anomer: white solid,
mp 107-108 °C (lit. mp 101 °C); Rf ) 0.65 (33% ethyl acetate in
hexane); [R]20 ) +49° (c ) 0.6, CHCl3) (lit. [R]23 ) +57.1°, c )
D
D
1.97, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.4-7.1 (m, 35 H), 4.98
(d, 1 H, J ) 3.7 Hz, H 1), 4.96 (d, 1 H, J ) 11.0 Hz), 4.94 (d, 1 H,
J ) 10.9 Hz), 4.91 (d, 1 H, J ) 11.0 Hz), 4.82 (d, 1 H, J ) 11.0 Hz),
4.81 (d, 1 H, J ) 10.9 Hz), 4.77 (d, 1 H, J ) 10.9 Hz), 4.71 (d, 1 H,
J ) 11.9 Hz), 4.66 (s, 2 H), 4.64 (d, 1 H, J ) 11.3 Hz), 4.57 (d, 1 H,
J ) 12.1 Hz), 4.57 (d, 1 H, J ) 12.0 Hz), 4.55 (d, 1 H, J ) 3.5 Hz,
H 1′), 4.45 (d, 1 H, J ) 11.0 Hz), 4.42 (d, 1 H, J ) 12.1 Hz), 3.98 (t,
1 H, J ) 9.3 Hz), 3.95 (t, 1 H, J ) 9.3 Hz), 3.79 (m, 3 H), 3.71 (dd,
1 H, J ) 11.3, 2.7 Hz), 3.65 (m, 3 H), 3.55 (dd, 1 H, J ) 10.7, 2.2
Hz), 3.54 (dd, 1 H, J ) 9.7, 3.5 Hz), 3.44 (dd, 1 H, J ) 9.6, 3.6 Hz),
3.35 (s, 3 H); 13C NMR (126 MHz, CDCl3) δ 138.8, 138.5, 138.4,
138.2, 138.1, 128.4, 128.4, 128.3, 128.3, 128.0, 128.0, 127.9, 127.9,
127.8, 127.7, 127.6, 127.6, 127.6, 127.5, 127.5, 98.0, 97.3, 82.2, 81.7,
80.1, 80.0, 77.8, 77.6, 75.7, 75.5, 75.0, 74.9, 73.4, 72.3, 70.4, 70.2,
68.5, 66.0, 55.1; FTIR (neat film) 3030, 2924, 1453, 1159, 1136, 1028,
736 cm-1; HRMS (FAB) m/z calcd for C62H65O11 (M - H) 985.4527,
found 985.4531. Anal. Calcd for C62H66O11: C, 75.43; H, 6.74.
Found: C, 75.30; H, 6.78. â-Anomer: white solid; mp 128-130 °C
dichloromethane); [R]20 ) +20° (c ) 1.0, CHCl3) (lit. [R]23
)
D
D
+24.2°, c ) 2.23, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.49-7.20
(m, 35 H), 5.14 (d, 1 H, J ) 11.1 Hz), 4.91 (d, 1 H, J ) 10.8 Hz), 4.85
(d, 1 H, J ) 11.02 Hz), 4.85 (d, 1 H, J ) 11.1 Hz), 4.84 (s, 1 H), 4.83
(d, 1 H, J ) 11.05 Hz), 4.80 (d, 1 H, J ) 10.6 Hz), 4.80 (d, 1 H, J )
11.4 Hz), 4.65 (d, 1 H, J ) 12.2 Hz), 4.62 (d, 1 H, J ) 12.0 Hz), 4.62
(d, 1 H, J ) 3.7 Hz, H 1′), 4.60 (d, 1 H, J ) 11.0 Hz), 4.48 (d, 1 H,
J ) 12.0 Hz), 4.44 (d, 1 H, J ) 11.8 Hz), 4.43 (d, 1 H, J ) 7.9 Hz,
H 1), 4.42 (d, 1 H, J ) 12.0 Hz), 4.01 (dd, 1 H, J ) 10.0, 9.0 Hz),
3.90 (t, 1 H, J ) 9.2 Hz), 3.89 (dd, 1 H, J ) 11.0, 3.3 Hz), 3.88 (dd,
1 H, J ) 11.0, 3.2 Hz), 3.76 (dd, 1 H, J ) 11.0, 1.9 Hz), 3.65 (dd, 1
H, J ) 9.8, 8.8 Hz), 3.64 (dd, 1 H, J ) 9.8, 2.8 Hz), 3.59 (dd, 1 H, J
) 11.2, 4.8 Hz), 3.53 (dd, 1 H, J ) 10.9, 2.0 Hz), 3.51 (t, 1 H, J ) 8.9
Hz), 3.51 (m, 1 H), 3.41 (dd, 1 H, J ) 9.0, 7.9 Hz), 3.41 (s, 3H), 3.34
(ddd, 1 H, J ) 9.8, 4.6, 1.8 Hz); 13C NMR (126 MHz, CDCl3) δ 139.8,
138.8, 138.8, 138.6, 138.6, 138.1, 128.7, 128.6, 128.6, 128.5, 128.4,
128.3, 128.2, 128.2, 128.0, 128.0, 127.9, 127.8, 127.8, 127.7, 127.5,
127.3, 102.7, 98.6, 85.1, 83.0, 80.6, 79.0, 78.3, 76.9, 76.8, 75.8, 75.6,
75.4, 75.1, 75.0, 73.8, 73.6, 73.5, 70.2, 70.1, 69.2, 68.1, 55.5; FTIR
(neat film) 3028, 2926, 1453, 1156, 1095, 1028, 734 cm-1; HRMS
(FAB) m/z calcd for C62H65O11 (M - H) 985.4527, found 985.4531.
(lit. mp 133-135 °C); Rf ) 0.61 (33% ethyl acetate in hexane); [R]20
D
) +18.5° (c ) 1.3, CHCl3) (lit. [R]23 ) +18.6°, c ) 0.49, CHCl3);
D
1H NMR (500 MHz, CDCl3) δ 7.4-7.1 (m, 35 H), 4.97 (d, 1 H, J )
11.0 Hz), 4.96 (d, 1 H, J ) 10.7 Hz), 4.90 (d, 1 H, J ) 10.8 Hz), 4.79
(m, 4 H), 4.74 (d, 1 H, J ) 11.2 Hz), 4.71 (d, 1 H, J ) 11.1 Hz), 4.65
(d, 1 H, J ) 12.1 Hz), 4.60 (d, 1 H, J ) 3.4 Hz, H 1′), 4.58 (d, 1 H,
J ) 10.9 Hz), 4.52 (m, 3 H), 4.34 (d, 1 H, J ) 7.8 Hz, H 1), 4.18 (dd,
1 H, J ) 10.6, 2.0 Hz), 3.98 (t, 1 H, J ) 9.3 Hz), 3.82 (m, 1 H), 3.72
(dd, 1 H, J ) 11.1, 1.7 Hz), 3.67 (dd, 1 H, J ) 10.8, 4.9 Hz), 3.62 (t,
1 H, J ) 9.0 Hz), 3.56 (t, 1 H, J ) 9.4 Hz), 3.51 (m, 3 H), 3.42 (m,
1 H), 3.32 (s, 3 H); 13C NMR (126 MHz, CDCl3) δ 138.8, 138.4, 138.4,
138.1, 137.9, 128.4, 128.3, 128.2, 128.0, 127.8, 127.8, 127.7, 127.7,
127.6, 127.5, 97.9, 97.2, 82.1, 81.6, 80.1, 79.9, 77.7, 77.5, 75.7, 75.5,
75.0, 74.9, 73.4, 72.3, 70.3, 70.2, 68.4, 66.0, 55.1; FTIR (neat film)
3029, 2945, 1497, 1388, 1068, 739 cm-1; HRMS (FAB) m/z calcd for
C62H65O11 (M - H) 985.4527, found 985.4531. Anal. Calcd for
C62H66O11: C, 75.43; H, 6.74. Found: C, 75.59; H, 6.79.
Methyl-O-(2,3,4,6-tetra-O-benzoyl-â-D-glucopyranosyl)-(1 f 4)-
2,3,6-tri-O-benzyl-r-D-glucopyranoside (18). Viscous oil; Rf ) 0.54
(15% ethyl acetate in benzene); [R]20 ) +1° (c ) 1.5, CHCl3) (lit.
D
1
[R]25 ) +1°, c ) 1.0, CHCl3); H NMR (500 MHz, CDCl3) δ 8.0-
Methyl-O-(2,3,4,6-Tetra-O-benzoyl-â-D-glucopyranosyl)-(1 f 6)-
2,3,4-tri-O-benzyl-r-D-glucopyranoside (16). Viscous oil; Rf ) 0.40
D
7.2 (m, 35 H), 5.62 (t, 1 H, J ) 9.5 Hz), 5.55 (t, 1 H, J ) 9.6 Hz),
5.46 (dd, 1 H, J ) 9.6, 8.0 Hz), 5.07 (d, 1 H, J ) 11.2 Hz), 4.81 (d,
1 H, J ) 11.1 Hz), 4.78 (d, 1 H, J ) 8.1 Hz, H 1), 4.76 (d, 1 H, J )
12.9 Hz), 4.75 (d, 1 H, J ) 12.4 Hz), 4.60 (d, 1 H, J ) 12.2 Hz), 4.56
(d, 1 H, J ) 3.5 Hz, H 1′), 4.40 (dd, 1 H, J 12.1, 3.6 Hz), 4.34 (d, 1
H, J ) 12.2 Hz), 4.26 (dd, 1 H, J ) 12.1, 5.0 Hz), 3.96 (t, 1 H, J )
9.4 Hz), 3.88 (t, 1 H, J ) 9.1 Hz), 3.73 (m, 2 H), 3.50 (m, 1 H), 3.46
(dd, 1 H, J ) 9.5, 3.7 Hz), 3.42 (dd, 1 H, J ) 10.7, ∼1 Hz), 3.28 (s,
3 H); 13C NMR (126 MHz, CDCl3) δ 166.1, 165.8, 165.1, 164.9, 145.6,
139.3, 138.4, 137.9, 133.4, 133.4, 133.2, 133.0, 131.1, 129.8, 129.7,
129.7, 129.4, 129.1, 128.9, 128.9, 128.5, 128.4, 128.4, 128.3, 128.1,
127.8, 127.4, 127.2, 124.8, 100.4, 98.5, 80.0, 78.8, 77.3, 75.4, 73.6,
73.6, 73.2, 72.3, 71.8; FTIR (neat film) 3032, 2939, 1736, 1731, 1601,
1451, 1265, 1093, 710 cm-1; HRMS (FAB) m/z calcd for C62H57O15
(M - H) 1041.3697, found 1041.3693. Anal. Calcd for C62H58O15: C,
71.39; H, 5.60. Found: C, 71.08; H, 5.73.
(33% ethyl acetate in hexane); [R]20 ) +18° (c ) 1.4, CHCl3) (lit.
D
1
[R]21 ) +19.6°, c ) 1.0, CHCl3); H NMR (500 MHz, CDCl3) δ
D
7.99 (m, 1 H), 7.88 (m, 1 H), 7.82 (m, 1 H), 7.6-7.0 (m, 35 H), 5.89
(t, 1 H, J ) 9.6 Hz), 5.68 (t, 1 H, J ) 9.69 Hz), 5.60 (dd, 1 H, J ) 9.6,
7.8 Hz), 4.90 (d, 1 H, J ) 10.89 Hz), 4.83 (d, 1 H, J ) 7.8 Hz, H 1),
4.74 (d, 1 H, J ) 12.1 Hz), 4.69 (d, 1 H, J ) 11.1 Hz), 4.61 (dd, 1 H,
J ) 12.1, 3.6 Hz), 4.60 (d, 1 H, J ) 12.1 Hz), 4.51 (m, 3 H, incorporates
H 1′), 4.29 (d, 1 H, J ) 11.1 Hz), 4.15 (d, 1 H, J ) 10.3 Hz), 4.15 (m,
1 H), 3.89 (t, 1 H, J ) 9.3 Hz), 3.74 (m, 2 H), 3.43 (dd, 1 H, J ) 9.6,
3.6 Hz), 3.83 (t, 1 H, J ) 9.3 Hz), 3.21 (s, 3 H); 13C NMR (126 MHz,
CDCl3) δ 166.2, 166.9, 165.2, 165.0, 138.8, 138.2, 138.1, 133.5, 133.3,
133.2, 133.1, 129.9, 129.8, 129.7, 129.6, 129.4, 129.2, 128.8, 128.7,
128.5, 128.4, 128.3, 128.3, 128.3, 128.3, 128.2, 127.9, 127.9, 127.6,
127.5, 127.5, 127.0, 124.8, 101.3, 98.0, 81.9, 79.8, 77.4, 75.6, 74.7,
73.4, 72.9, 72.2, 71.8, 69.8, 69.5, 68.3, 63.3, 55.0; FTIR (neat film)
3032, 2930, 1735, 1731, 1602, 1452, 1267, 1093, 710 cm-1; HRMS
(FAB) m/z calcd for C62H57O15 (M - H) 1041.3697, found 1041.3693.
Anal. Calcd for C62H58O15: C, 71.39; H, 5.60. Found: C, 71.08; H,
5.40.
2′,3′,5′-Tri-O-benzoylthymidine (19). Viscous oil; Rf ) 0.13 (33%
ethyl acetate in hexanes); [R]23D ) -102° (c ) 1.7, CHCl3); 1H NMR
(500 MHz, C6D6) δ 8.12 (m, 2 H), 7.88 (m, 2 H), 7.84 (m, 2 H), 7.66
(m, 1 H), 7.56-7.48 (m, 4 H), 7.40-7.26 (m, 5 H), 6.47 (d, 1 H, J )
9.6 Hz, H 1), 6.31 (t, 1 H, J ) 2.6 Hz), 5.55 (m, 1 H), 5.49 (dt, 1 H,
J ) 9.8, 2.7 Hz), 4.33 (dd, 1 H, J ) 11.0, 5.7 Hz), 4.24 (t, 1 H, J )
11.0 Hz),1.95 (s, 3 H); 13C NMR (126 MHz, CDCl3) δ 165.41, 165.11,
164.85, 134.49, 133.84, 133.78, 133.66, 129.98, 129.87, 129.25, 128.86,
(31) (a) Kim, W.-S.; Hosono, S.; Sasai, H.; Shibasaki, M. Heterocycles
1996, 42, 795-809. (b) Fukase, K.; Hasuoka, A.; Kinoshita, I.; Aoki, Y.;
Kusumoto, S. Tetrahedron 1995, 51, 4923. (c) Koide, K.; Ohno, M.;
Kobayashi, S. Tetrahedron Lett. 1991, 48, 7065-7068.