Conformational Arming of Thioglycosides by Silylation
A R T I C L E S
(dd, J ) 5.9 Hz, 6.2 Hz, 1H), 3.82 (dd, J ) 3.9 Hz, 9.7 Hz, 1H), 3.74
(dd, J ) 1.6 Hz, 10.8 Hz, 1H), 3.71 (t, J ) 8.5 Hz, 1H), 3.69 (dd, J )
4.6 Hz, 10.4 Hz, 1H), 3.63 (dd, J ) 4.9 Hz, 5.5 Hz, 1H), 3.62 (bd, J
) 8.5 Hz, 1H), 3.50 (m, 1H), 3.48 (dd, J ) 8.9 Hz, 9.6 Hz, 1H), 3.45
(dd, J ) 8.9 Hz, 9.5 Hz, 1H); 13C NMR (400 MHz, CDCl3, 50 °C): δ
138.3, 137.9, 137.8, 137.7, 133.6, 131.5, 129.1, 128.6, 128.6, 128.5,
128.4, 128.3, 128.1, 128.0, 127.9, 127.9, 127.9, 127.8, 127.8, 127.6,
99.2 (JC-H ) 170 Hz), 87.1, 86.7, 81.1, 78.2, 77.9, 75.9, 75.6, 75.1,
73.7, 71.3, 70.3, 70.1, 69.8, 68.8, 67.4; HRMS(ES) m/z calcd for
C46H50O10SNa: 817.3022, m/z found: 817.3008.
73.4, 69.2, 68.5, 68.0, 67.8, 67.7, 67.5, 20.8 (2C), 20.7; HRMS(ES)
m/z calcd for C52H56O13SNa: 943.3339, found 943.3337.
Phenyl 2,3,4-tri-O-benzyl-6-O-(6-deoxy-2,3,4-tri-O-tert-butyldi-
methylsilyl-r-L-mannopyranosyl)-1-thio-â-D-glucopyranoside
(17r): [R]RTD -16.2° (c 1, CHCl3); 1H NMR (400 MHz, (CDCl3): δ
7.56 (bd, J ) 6.9 Hz, 2H), 7.42-7.15 (m, 18H), 4.90 (d, J ) 11.0 Hz,
1H), 4.89 (bd, J ) 9.2 Hz, 1H), 4.90-4.83 (m, 1H), 4.84 (d, J ) 11.2
Hz, 1H), 4.71 (d, J ) 10.3 Hz, 1H), 4.62 (d, J ) 9.7 Hz, 1H), 4.58 (d,
J ) 9.7 Hz, 1H), 3.97 (bm, 2H), 3.91 (dd, J ) 2.2 Hz, 3.0 Hz, 1H),
3.78 (bm, 1H), 3.70 (t, J ) 8.7 Hz, 1H), 3.70 (m, 1H), 3.59 (bm, 1H),
3.55-3.33 (m, 3H), 1.21 (d, J ) 6.2 Hz, 3H), 0.95-0.90 (bm,
18H), 0.90 (s, 9H), 0.17-0.05 (m, 18H); 13C NMR (400 MHz,
(CDCl3): δ 138.8, 138.4, 138.3, 134.0 (b), 132.3 (b), 129.0-127.5
(multiple peaks), 100.8 (b), 87.6, 87.4, 87.0 (b), 81.3 (b), 79.0 (b),
78.3 (b), 75.8, 75.7, 75.6, 75.5, 75.4, 75.3, 75.2, 75.1, 75.0, 73.6 (b),
71.2 (b), 26.3 (b), 26.0 (b), 18.9 (b), 18.4, 18.3 (b), -2.4(b), -3.8 (b)
-3.9, -4.0; HRMS(ES) m/z calcd for C57H86O9SSi3Na: 1053.5198,
m/z found: 1053.5175.
Phenyl 2,3,6-tri-O-benzyl-4-O-(6-O-benzyl-2,3,4-tri-O-tert-bu-
tyldimethylsilyl-r-D-galactopyranosyl)-1-thio-â-D-glucopyrano-
side (25r): [R]RT 23.2° (c 2.0, CHCl3); 1H NMR (400 MHz,
D
(CDCl3): δ 7.55 (m, 2H), 7.43-7.09 (m, 23H), 5.24 (d, J ) 2.5 Hz,
0.22H, a), 5.10 (s, 0.78H, b), 4.85 (d, J ) 12.2 Hz, 1H), 4.79 (d, J )
12.2 Hz, 1H), 4.79 (d, J ) 9.9 Hz, 1H), 4.67 (d, J ) 9.8 Hz, 1H), 4.59
(d, J ) 11.7 Hz, 1H), 4.56 (d, J ) 12.2 Hz, 1H), 4.53 (d, J ) 12.2 Hz,
1H), 4.50 (d, J ) 11.6 Hz, 1H), 4.47 (d, J ) 9.9 Hz, 1H), 4.29 (d, J
) 1.50 Hz, 0.22H, a), 4.21 (dd, J ) 2.5 Hz, 5.8 Hz, 0.78H, b), 4.15
(bd, J ) 11.0 Hz, 0.78H, b), 4.06 (m, 0.78H, b), 3.89 (m, 0.22H, a),
3.80, 3.68 (m, 2H), 3.69-3.63 (m, 1.3H), 3.60 (t, J ) 8.7 Hz, 0.78H,
b), 3.59-3.56 (m, 1H), 3.52 (bddd, J ) 1.7 Hz, 7.9 Hz, 9.7 Hz, 0.78H,
b), 3.45 (dd, J ) 8.8 Hz, 9.6 Hz, 0.78H, b), 3.40 (t, J ) 4.9 Hz, 0.22H,
a), 3.30 (dd, J ) 8.4 Hz, 9.4 Hz, 0.22H, a), 0.88, 0.87, 0.85 (3 s, 6H,
a), 0.86, 0.85 (2 s, 14H, b), 0.64 (s, 7H), 0.08, 0.07, 0.05, 0.04, 0.01,
0.00, -0.06, -0.18 (8 s, 18H); 13C NMR (400 MHz, (50 °C, CDCl3):
δ 139.0, 138.8, 138.8, 137.9, 134.5, 131.4, 128.9, 128.5, 128.4 (3C),
128.3, 128.3, 127.8, 127.7, 127.7, 127.6, 127.3, 127.2, 126.7, 93.8
(broad), 87.5, 86.6, 81.1, 79.4, 76.6 (broad), 75.4 (broad), 75.0 (broad),
74.6 (broad), 74.4 (broad), 73.4, 73.1, 72.5 (broad), 70.7, 67.6 (broad),
66.4 (broad), 26.1, 25.9, 25.8, 18.3, 18.2, 17.9, -4.1, -4.1, -4.5, -4.7,
-4.8, -4.9; HRMS(ES) m/z calcd for C64H92O10SSi3Na: 1159.5617,
m/z found: 1159.5604.
Phenyl 2,3,4-tri-O-benzyl-6-O-(6-deoxy-r-L-mannopyranosyl)-1-
1
thio-â-D-glucopyranoside (17u): [R]RT -15.8° (c 0.9, CHCl3); H
D
NMR (400 MHz, (CDCl3): δ 7.55 (m, 2H), 7.40 (m, 2H), 7.37-7.18
(m, 16H), 4.92 (d, J ) 10.9 Hz, 1H), 4.90 (d, J ) 10.1 Hz, 1H), 4.85
(2 d, J ≈ 11 Hz, 2H), 4.73 (d, J ) 11.0 Hz, 1H), 4.72 (bs, 1H, H1),
4.66 (d, J ) 9.8 Hz, 1H, H1′), 4.57 (d, J ) 11.1 Hz, 1H), 3.94 (bd, J
) 9.8 Hz, 1H), 3.89 (bs, 1H), 3.83 (dd, J ) 3.2 Hz, 9.4 Hz, 1H), 3.74
(dd, J ) 6.5 Hz, 9.3 Hz, 1H), 3.71 (bd, J ) 8.8 Hz, 1H), 3.55 (bdd, J
) 4.4 Hz, 6.4 Hz, 1H), 3.53-3.44 (m, 4H), 1.30 (d, J ) 6.2 Hz, 3H);
13C NMR (400 MHz, (CDCl3): δ 138.0, 137.7, 137.6, 133.3, 131.7,
128.7, 128.2, 128.2, 128.2, 127.9, 127.7, 127.7, 127.6, 127.5, 127.5,
127.4, 99.6 (JCH ) 167.5 Hz), 87.1, 86.5, 80.7, 78.1, 76.5, 75.6, 75.2,
74.8, 72.9, 71.5, 70.6, 67.8, 65.9, 17.3: HRMS(ES) m/z calcd for
C39H44O9SNa: 711.2604, m/z found: 711.2604.
Phenyl 2,3,6-tri-O-benzyl-4-O-(6-deoxy-2,3,4-tri-O-tert-butyldi-
methylsilyl-r-L-mannopyranosyl)-1-thio-â-D-glucopyranoside
Phenyl 2,3,4-tri-O-benzyl-4-O-(6-O-benzyl-r-D-galactopyranosyl)-
1
(18r): [R]RT -32.3° (c 0.8, CHCl3); H NMR (400 MHz, (CDCl3):
D
1
1-thio-â-D-glucopyranoside (25u): [R]RT +25.5 (c 0.6, CHCl3); H
D
δ 7.56 (d, J ) 6.8 Hz, 2H), 7.40-7.10 (m, 18H), 5.08 (d, J ) 10.4
Hz, 1H), 4.92 (d, J ) 7.3 Hz, 1H), 4.78 (d, J ) 10.2 Hz, 1H), 4.74 (d,
J ) 10.4 Hz, 1H), 4.74 (d, J ) 10.4 Hz, 1H), 4.63 (d, J ) 9.8 Hz,
1H), 4.59 (d, J ) 11.9 Hz, 1H), 4.55 (d, J ) 11.9 Hz, 1H), 3.99 (t, J
) 9.5 Hz, 1H), 3.88 (dd, J ) 2.1 Hz, 7.6 Hz, 1H), 3.85-3.75 (m, 4H),
3.69 (m, 1H), 3.60 (t, J ) 9.0 Hz, 1H), 3.49-3.40 (m, 2H), 1.09 (d, J
) 6.85 Hz, 3H), 0.91, 0.86, 0.85 (3 s, 27H), 0.11, 0.08, 0.07, 0.07,
0.04, 0.02 (6 s, 18H); 13C NMR (400 MHz, (CDCl3): δ 138.8, 138.7,
138.5, 133.6, 132.3, 128.9, 128.5, 128.4, 128.3 (2 C), 128.2, 127.8,
127.6, 127.5 (2C), 127.3, 96.8, 87.2, 85.4, 80.2, 80.0, 76.9, 76.6, 76.1,
75.5, 74.0, 74.0, 73.3, 71.5, 68.5, 26.3, 25.9, 25.8, 18.5, 18.3, 18.2,
18.0, -3.9, -4.0, -4.3, -4.3, -4.4, -4.7; HRMS(ES) m/z calcd for
C57H86O9SSi3Na: 1053.5198, m/z found: 1053.5217.
NMR (400 MHz, (CDCl3): δ 7.58 (m, 2H), 7.41-7.20 (m, 23H), 5.24
(d, J ) 3.7 Hz, 1H), 5.00 (d, J ) 11.0 Hz, 1H), 4.96 (d, J ) 10.2 Hz,
1H), 4.71 (d, J ) 11.0 Hz, 1H), 4.65 (d, J ) 9.4 Hz, 1H), 4.65 (d, J
) 11.0 Hz, 1H), 4.59 (d, J ) 11.8 Hz, 1H), 4.53 (d, J ) 11.9 Hz, 1H),
4.50 (d, J ) 11.8 Hz, 1H), 4.49 (d, J ) 11.9 Hz, 1H), 3.98 (m, 1H),
3.94 (dd, J ) 5.5 Hz, 5.7 Hz, 1H), 3.91 (dd, J ) 4.1 Hz, 10.9 Hz, 1H),
3.88 (t, J ) 9.2 Hz, 1H), 3.78 (dd, J ) 1.7 Hz, 10.9 Hz, 1H), 3.70-
3.62 (m, 3H), 3.62 (t, J ) 8.7 Hz, 1H), 3.57 (t, J ) 8.7 Hz, 1H), 3.48
(dd, J ) 3.1 Hz, 10.0 Hz, 1H), 3.44 (bd, J ) 9.5 Hz, 1H); 13C NMR
(400 MHz, (CDCl3): δ 138.4, 137.9, 137.6, 137.3, 133.6, 132.1, 129.1,
128.7, 128.6, 128.5, 128.4, 128.3, 128.3 (2 C), 128.1, 127.9, 127.8,
127.7, 127.7, 127.6, 100.8, 87.4, 85.2, 81.1, 79.3, 76.5, 75.5, 75.1, 73.8,
73.3, 71.0, 70.2, 70.1, 70.1, 69.5, 68.8; HRMS(ES) m/z calcd for
C46H50O10SNa: 817.3022, m/z found: 817.3051.
Phenyl 2,3,6-tri-O-benzyl-4-O-(6-deoxy-r-L-mannopyranosyl)-1-
1
thio-â-D-glucopyranoside (18u): [R]RT -26.5 (c 1.8, CHCl3); H
D
Phenyl 2,3,4-tri-O-benzyl-4-O-(6-O-benzyl-2,3,4-tri-O-acetyl-r-
D-galactopyranosyl)-1-thio-â-D-glucopyranoside (25a): [R]RTD +26.7
(c 0.5, CHCl3); 1H NMR (400 MHz, (CDCl3): δ 7.57 (m, 2H), 7.40-
7.14 (m, 23H), 5.72 (d, J ) 3.6 Hz, 1H), 5.50 (dd, J ) 1.2, 3.1 Hz,
1H), 5.30 (dd, J ) 3.1, 11.0 Hz, 1H), 5.23 (dd, J ) 3.6, 11.0 Hz, 1H),
4.93 (d, J ) 11.1 Hz, 1H), 4.91 (d, J ) 10.3 Hz, 1H), 4.67 (d, J )
10.3 Hz, 1H), 4.65 (d, J ) 11.1 Hz, 1H), 4.62(d, J ) 9.7 Hz, 1H),
4.62 (d, J ) 12.1 Hz, 1H), 4.57 (d, J ) 12.1 Hz, 1H), 4.44 (d, J )
11.9 Hz, 1H), 4.20 (bt, J ≈ 6 Hz, 1H), 4.18 (d, J ) 11.9 Hz, 1H), 4.03
(t, J ) 9.1 Hz, 1H), 3.89 (dd, J ) 4.1, 11.2 Hz, 1H), 3.79 (dd, J ) 1.9,
11.2 Hz, 1H), 3.71 (t, J ) 8.6 Hz, 1H), 3.55 (dd, J ) 8.7, 9.7 Hz, 1H),
3.53 (m, 1H), 3.34 (dd, J ≈ 6, 9 Hz, 1H), 3.31 (dd, J ≈ 6, 9 Hz, 1H),
2.00 (s, 3H), 1.96 (s, 3H), 1.85 (s, 3H); 13C NMR (400 MHz, (CDCl3):
δ 170.2, 170.1, 170.1, 138.5, 138.1, 137.9, 137.7, 133.7, 132.1, 129.0,
128.5, 128.5, 128.5, 128.3, 128.2, 128.0, 128.0, 127.9, 127.8, 127.7,
127.6, 127.6, 127.2, 96.3, 87.4, 86.4, 81.1, 78.8, 75.2, 74.8, 73.5, 73.4,
NMR (400 MHz, (CDCl3): δ 7.49 (m, 2H), 7.30-7.15 (m, 18H), 4.90
(d, J ) 11.0 Hz, 1H), 4.90 (bs, 1H, H1), 4.82 (d, J ) 10.1 Hz, 1H),
4.67 (d, J ) 11.0 Hz, 1H), 4.59 (d, J ) 10.1 Hz, 1H), 4.58 (d, J ) 9.1
Hz, 1H, H1′), 4.54 (d, J ) 11.9 Hz, 1H), 4.48 (d, J ) 11.9 Hz, 1H),
3.80 (t, J ) 9.15 Hz, 1H), 3.71-3.67 (m, 2H), 3.66 (bs, 1H), 3.59 (dd,
J ) 3.9 Hz, 11.1 Hz, 1H), 3.53-3.45 (m, 3H), 3.32 (ddd, J ) 2.7 Hz,
3.0 Hz, 9.5 Hz, 1H), 3.22 (dd, J ) 9.2 Hz, 9.6 Hz, 1H), 0.87 (d, J )
6.1 Hz, 3H); 13C- NMR (400 MHz, (CDCl3): δ 138.5, 138.0, 137.9,
133.8, 132.2, 129.1, 128.6 (3 C), 128.5, 128.4, 128.1, 128.1, 127.9,
127.7, 127.6, 100.1 (JCH ) 167 Hz), 87.8, 85.0, 81.3, 79.3, 75.5, 75.4,
75.0, 73.8, 73.5, 71.8, 71.0, 69.1, 68.6, 17.4; HRMS(ES) m/z calcd for
C39H44O9SNa: 711.2604, m/z found: 711.2623.
Phenyl 2,3-Di-O-benzoyl-6-O-benzyl-4-O-(6-deoxy-2,3,4-tri-O-tert-
butyldimethylsilyl-r-L-mannopyranosyl)-1-thio-â-D-glucopyrano-
side (22r). The standard procedure was followed with the exception
that 1.5 equiv of donor was used.
9
J. AM. CHEM. SOC. VOL. 129, NO. 29, 2007 9233