1664
T. Ziegler et al.
PAPER
Phenyl 3-O-Benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-1-thio-b-D-galactopyranoside (4a)
13C NMR (CDCl3) d = 61.4 (C-6), 64.7 (C-3), 70.3 (C-4), 73.4 (C-
5), 74.8 (C-2), 101.6 (C-1).
Treatment of 2a (266 mg, 0.52 mmol) according to the General Pro-
Anal. Calcd for C26H44O8Si2: C, 57.75; H, 8.20. Found C, 57.67; H,
8.18.
20
cedure II afforded 3a (24 mg, 8%) and 4a (250 mg, 77%); [a]D
12.9 (c = 1.1, CHCl3).
–
Methyl 2-O-Benzyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-a-D-glucopyranoside (5)
1H NMR (CDCl3): d = 3.95–3.77 (m, 3 H, H-5,6a,6b), 4.06 (t, 1 H,
2,3 = 9.8 Hz, H-2), 4.55 (d, 1 H, H-4), 4.60 (d, 1 H, J1,2 = 9.5 Hz, H-
J
Treatment of 2b (437 mg, 1.0 mmol) according to the General Pro-
1),5.14 (t, 1 H, J3,4 = 2.8 Hz, H-3).
13C NMR (CDCl3): d = 59.1 (C-6), 66.4 (C-2), 66.7 (C-4), 77.1 (C-
3), 77.9 (C-5), 88.3 (C-1).
cedure III afforded 5 (480 mg, 91%); [a]D20 +47.8 (c = 1.1, CHCl3).
1H NMR (CDCl3) d = 3.51–3.47 (m, 1 H, H-5), 3.36 (dd, 1 H, H-2),
3.77 (t, 1 H, J3,4 = J4,5 = 9.2 Hz, H-4), 3.85 (dd, 1 H, J5,6b = 1.3 Hz,
H-6b), 3.94 (t, 1 H, J2,3 = J3,4 = 9.2 Hz, H-3), 4.11 (dd, 1 H,
Anal. Calcd for C31H46O7SSi2: C, 60.16; H, 7.49. Found C, 60.08;
H, 7.51.
J5,6a = 1.9 Hz, H-6a), 4.63 (d, 1 H, J1,2 = 4.0 Hz, H-1).
Methyl 2-O-Benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-a-D-glucopyranoside (3b)
13C NMR (CDCl3): d = 60.7 (C-6), 69.3 (C-4), 71.4 (C-5), 73.1 (C-
3), 79.9 (C-2), 98.0 (C-1).
Treatment of 2b (437 mg, 1.0 mmol) according to the General Pro-
Anal. Calcd for C26H46O7Si2: C, 59.28; H, 8.80. Found C, 59.05; H,
8.72.
cedure I afforded 3b (481mg, 89%); [a]D20 +72.5 (c = 1.7, CHCl3).
1H NMR (CDCl3): d = 3.95–3.77 (m, 3 H, H-5,6a,6b), 4.06 (t, 1 H,
Methyl 3-O-Acetyl-2-O-benzyl-4,6-O-(1,1,3,3-tetraisopropyl-
1,3-disiloxane-1,3-diyl)-a-D-glucopyranoside (6)
J2,3 = 9.8 Hz, H-2), 4.55 (d, 1 H, H-4), 4.60 (d, 1 H, J1,2 = 9.5 Hz, H-
1), 5.14 (t, 1 H, J3,4 = 2.8 Hz, H-3).
13C NMR (CDCl3): d = 59.1 (C-6), 66.4 (C-2), 66.7 (C-4), 77.1 (C-
3), 77.9 (C-5), 88.3 (C-1).
Treatment of 5 (110 mg, 210 µmol) according to the General Proce-
dure IV afforded 6 (93 mg, 73%); [a]D20+67.0 (c = 0.7, CHCl3).
1H NMR (CDCl3) d = 3.41 (dd, 1 H, H-2), 3.58 (d, 1 H, J = 9.6 Hz,
H-5), 3.87 (dd, 1 H, J5,6b = 1.3 Hz, H-6b), 3.90 (t, 1 H,
Anal. Calcd for C26H43O8Si2: C, 57.75; H, 8.20. Found C, 57.60; H,
8.20.
J
3,4 = J4,5 = 9.4 Hz, H-4), 4.13 (dd, 1 H, J5,6a = 2.0 Hz, J6a,6b = 12.7
Hz, H-6a), 4.68 (d, 1 H, J1,2 = 3.6 Hz, H-1), 5.43 (t, 1 H,
2,3 = J3,4 = 9.6 Hz, H-3).
Methyl 3-O-Benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-a-D-glucopyranoside (4b)
Treatment of 2b (437 mg, 1 mmol) according to the General Proce-
dure II afforded first 3b (336 mg, 62%). Compound 4b was eluted
next (119 mg, 22%); [a]D20 +51.5 (c = 1.0, CHCl3).
1H NMR (CDCl3): d = 1.15-0.56 (m, 28 H, TIPS), 2.14 (s, 1 H, OH),
3.44 (s, 3 H, CH3), 3.66 (d, 1 H, J5,4 = 9.5 Hz, H-5), 3.69 (dd, 1 H,
J
13C NMR (CDCl3): d = 60.7 (C-6), 67.7 (C-3), 71.7 (C-5), 73.5 (C-
4), 78.2 (C-2), 97.9 (C-1).
Anal. Calcd for C28H48O8Si2: C, 59.12; H, 8.50. Found C, 58.77; H,
8.50.
Methyl 3-O-Benzyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-a-D-mannopyranoside (7)
J2,1 = 4.0 Hz, J2,3 = 9.7 Hz, H-2), 3.95 (dd, 1 H, J5,6b = 1.3 Hz, H-6b),
4.09 (t, 1 H, J3,4 = 9.4 Hz, H-4), 4.18 (dd, 1 H, J5,6a = 1.9 Hz,
Treatment of 2c (437 mg, 1.0 mmol) according to the General Pro-
J6a,6b = 12.6, H-6a), 4.85 (d, 1 H, J1,2 = 3.9 Hz, H-1), 5.50 (t, 1 H,
cedure III afforded 7 (481 mg, 91%); [a]D20+44.4 (c = 1.0, CHCl3).
J3,4 = 9.6 Hz, H-3).
1H NMR (CDCl3) d = 3.47 (d, 1 H, J = 9.5 Hz, H-5), 3.71 (dd, 1 H,
H-3), 3.89 (dd, 1 H, J5,6b = 1.5 Hz, H-6b), 3.93 (dd, 1 H, J2,3 = 3.2
Hz, H-2), 4.15 (dd, 1 H, J5,6a = 2.0 Hz, J6a,6b = 12.6 Hz, H-6a), 4.21
(t, 1 H, J3,4 = J4,5 = 9.4 Hz, H-4), 4.78 (d, 1 H, J1,2 = 1.2 Hz, H-1).
13C NMR (CDCl3): d = 61.4 (C-6), 66.1 (C-4), 68.9 (C-2), 73.2 (C-
5), 80.0 (C-3), 101.2 (C-1).
13C NMR (CDCl3): d = 99.6 (C-1), 76.0 (C-2), 72.2 (C-4), 71.9 (C-
5), 67.1 (C-3), 60.7(C-6).
Anal. Calcd for C26H43O8Si2: C, 57.75; H, 8.20. Found C, 57.70; H,
8.20.
Methyl 2-O-Benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-a-D-mannopyranoside (3c)
Anal. Calcd for C26H45O7Si2: C,59.28; H, 8.80. Found C, 59.00;
H,8.80.
Treatment of 2c (1.60 g, 3.7 mmol) according to the General Proce-
dure I afforded 3c (1.32 g, 67%); [a]D20 –19.5 (c = 1.2, CHCl3).
Methyl 2-O-Acetyl-3-O-benzyl-4,6-O-(1,1,3,3-tetraisopropyl-
1,3-disiloxane-1,3-diyl)-a-D-mannopyranoside (8)
1H NMR (CDCl3): d = 3.58 (d, 1 H, J = 9.4, H-5), 3.94 (dd, 1 H,
J6b,5 = 1.1 Hz, H-6b), 4.14 (dd, 1 H, J2,3 = 3.8 Hz, J3,4 = 9.5 Hz,H-3),
Treatment of 7 (150 mg, 285 µmol) according to the General Proce-
4.20 (dd, 1 H, J6a,5 = 2.0 Hz, J6a,6b = 12.7 Hz, H-6a), 4.29 (t, 1 H,
J3,4 = J4,5 = 9.4 Hz, H-4), 4.85 (d, 1 H, J1,2 = 1.2 Hz, H-1), 5.42 (dd,
1 H, J1,2 = 1.5 Hz, J2,3 = 3.5 Hz, H-2).
13C NMR (CDCl3): d = 99.3 (C-1), 72.8 (C-2), 72.7 (C-3), 70.6 (C-
4), 67.6 (C-5), 60.9 (C-6).
dure IV afforded 8 (147 mg, 90%); [a]D20+17.9 (c = 1.5, CHCl3).
1H NMR (CDCl3) d = 3.50 (d, 1 H, J = 9.2 Hz, H-5), 3.81 (dd, 1 H,
H-3), 3.88 (dd, 1 H, J5,6b = 1.2 Hz, H-6b), 4.18 (dd, 1 H, J5,6a = 1.7
Hz, J6a,6b = 12.5 Hz, H-6a), 4.29 (t, 1 H, J3,4 = J4,5 = 9.6 Hz, H-4),
4.71 (d, 1 H, H-1), 5.28 (dd, 1 H, J1,2 = 1.8 Hz, J2,3 = 3.1 Hz, H-2).
Anal. Calcd for C26H44O8Si2: C, 57.75; H, 8.20. Found C, 57.67; H,
8.18.
13C NMR (CDCl3): d = 60.9 (C-6), 65.7 (C-4), 68.9 (C-2), 73.3 (C-
5), 76.7 (C-3), 99.1 (C-1).
Methyl 3-O-Benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disilox-
ane-1,3-diyl)-a-D-mannopyranoside (4c)
Treatment of 2c (437 mg, 1.0 mmol) according to the General Pro-
cedure II afforded first 3c (370 mg, 69%). Compound 4c was eluted
next (170 mg, 31%); [a]D20 –9.9 (c = 1.2, CHCl3).
Anal. Calcd for C28H47O8Si2: C, 59.12; H, 8.50. Found C, 59.24; H,
8.38.
Methyl 3-O-Allyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-
1,3-diyl)-a-D-mannopyranoside (9)
Treatment of 2c (437 mg, 1.0 mmol) according to the General Pro-
cedure III afforded 9 (399 mg, 84%); mp 113°C; [a]D20+34.5
(c = 1.1, CHCl3).
1H NMR (CDCl3): d = 3.42–3.37 (m, 1 H, H-5), 3.53 (dd, 1 H,
J3,4 = 9.3, H-3), 3.82 (dd, 1 H, J5,6b = 1.5, J6a,6b = 12.5 Hz, H-6b),
1H NMR (CDCl3): d = 3.67 (d, 1 H, J = 9.4 Hz, H-5), 3.95 (dd, 1 H,
J5,6b = 1.4 Hz, H-6b), 4.09 (dd, 1 H, H-2), 4.20 (dd, 1 H, J5,6a = 2.1
Hz, J6a,6b = 12.5 Hz, H-6a), 4.50 (t, 1 H, J3,4 = J4,5 = 9.7 Hz, H-4),
4.78 (d, 1 H, J1,2 = 1.7 Hz, H-1), 5.48 (dd, 1 H, J3,2 = 3.2 Hz,
J3,4 = 9.9 Hz, H-3).
Synthesis 1999, No. 9, 1661–1665 ISSN 0039-7881 © Thieme Stuttgart · New York