C-Glycosides
FULL PAPER
143 Hz; C(6’)), 70.5 (d, 1J(C,H)=144 Hz; C(5’)), 67.3 (d, 1J(C,H)=
142 Hz; C(3’)), 67.1 (d, 1J(C,H)=147 Hz; C(1’)), 66.9 (d, 1J(C,H)=
s, 36H; 36ꢃH C(SiC(CH3)3)), 0.16, 0.15, 0.14, 0.13, 0.120, 0.12, 0.11,
ꢀ
0.10 ppm (8ꢃs, 24H; 24ꢃH C(SiCH3)); 13C NMR (100.6 MHz, CDCl3):
ꢀ
1
1
138 Hz; C(4’)), 62.3 (t, J(C,H)=154 Hz; C(6)), 58.2 (t, J(C,H)=142 Hz;
C(7’)), 25.9, 25.89, 25.85, 25.7 (4ꢃq, 1J(C,H)=125 Hz; (CH3)3CSi), 18.2,
18.1, 17.9, 17.0 (4ꢃs; (CH3)3CSi), ꢀ4.4, ꢀ4.6, ꢀ4.7, ꢀ4.9, ꢀ5.0, ꢀ5.1,
d=137.6 (s; C(arom)), 129.6 (d, 1J(C,H)=159 Hz; C(arom)), 128.3 (d,
1J(C,H)=156 Hz; C(arom)), 127.3 (d, 1J(C,H)=156 Hz; C(arom)), 99.6
(d, 1J(C,H)=179 Hz; C(1)), 79.1 (d, 1J(C,H)=147 Hz; C(6’)), 73.6 (d,
1J(C,H)=159 Hz; C(5)), 73.4 (d, 1J(C,H)=154 Hz; C4’), 70.7 (d,
1J(C,H)=141 Hz; C(3’)), 69.0 (d, 1J(C,H)=144 Hz; C(1’)), 67.4 (d,
1J(C,H)=146 Hz; C(2’)), 67.3 (d, 1J(C,H)=146 Hz; C(5’)), 66.3 (t,
1J(C,H)=144 Hz; C(4)), 64.2 (d, 1J(C,H)=143 Hz; C(2)), 61.6 (t,
1J(C,H)=154 Hz; C(6)), 61.6 (q, 1J(C,H)=122 Hz; C(OCH3)), 58.5 (t,
1J(C,H)=143 Hz; C(7’)), 58.5 (t, 1J(C,H)=145 Hz; C(NCH2Ph)), 34.9 (d,
1J(C,H)=126 Hz; C(3)), 26.0, 25.9, 25.8, 25.7(4ꢃq, 1J(C,H)=125 Hz;
(CH3)3CSi), 18.3, 18.0, 17.9, 17.8 (4ꢃs; (CH3)3CSi), ꢀ4.4, ꢀ4.6, ꢀ4.8,
ꢀ4.9, ꢀ5.0, ꢀ5.1, ꢀ5.3, ꢀ5.5 ppm (8ꢃq, 1J(C,H)=118 Hz; CH3Si); IR
(film): n˜ =3477, 2953, 2856, 1714, 1633, 1471, 1256, 1099, 836, 778,
1
ꢀ5.3, ꢀ5.5 ppm (8ꢃq, J(C,H)=118 Hz; CH3Si); HRMS (MALDI-TOF):
m/z: calcd for C37H74O9Si4Na+: 797.4307; found: 797.4310; elemental
analysis calcd (%) for C37H74O9Si4 (775.32): C 57.32, H 9.62; found: C
57.24, H 9.56.
1,6-Anhydro-3-{(1R)-2,6-anhydro-3,4,5,7-tetrakis-O-[(tert-butyl)dimeth-
ylsilyl]-d-glycero-l-manno-heptitol-1-C-yl}-2-[(N-benzyl-N-methoxy)ami-
no]-2,3-dideoxy-b-d-xylo-hexopyran-4-ulose (6): A solution of 5 (200 mg,
0.258 mmol) in CH2Cl2 (1 mL) was stirred at RT, and BnNHOMe
(120 mg, 0.876 mmol) was added. The mixture was allowed to stir at am-
bient temperature for 12 h. Slow chromatography on silica gel (light pe-
troleum ether/diethyl ether 9:1) afforded 6 (193 mg, 82%) as a colorless
oil; Rf =0.61 (PE/diethyl ether 4:1); [a]2D5 =ꢀ1.7 (c=0.40 in CHCl3); 1H
NMR (400 MHz, CDCl3): d=7.46–7.43 (m, 2H; ArH), 7.38–7.26 (m, 3H;
739 cmꢀ1 HRMS (MALDI-TOF): m/z: calcd for C45H87NO10Si4Na+:
;
936.5304; found: 936.5304; elemental analysis calcd for C45H87NO10Si4
(914.52): C 59.10, H 9.59, N 1.53; found: C 59.15, H 9.50, N 1.62.
ArH), 6.07 (s; H C(1)), 4.50 (dd, 3J(H-5,Hexo C(6))=5.8, 3J(H-5,Hendo
4-O-Acetyl-1,6-anhydro-3-{(1R)-1,3,4,5,7-penta-O-acetyl-2,6-anhydro-d-
glycero-l-manno-heptitol-1-C-yl}-2-[(N-benzyl-N-methoxy)amino]-2,3-di-
deoxy-b-d-galacto-hexopyranose (8): Compound 7 (1.12 g, 1.22 mmol)
was dissolved in THF (3 mL), a solution of TBAF in THF (8 mLg,
9.76 mmol) was added, and the resulting solution was stirred for 3 h at
208C. The mixture was evaporated to dryness, and the residue was then
dissolved in pyridine (5 mL). A catalytic amount of DMAP was added,
followed by acetic anhydride (3 mL), and the solution was stirred for 2
days at 208C. MeOH (5 mL) was added, and the mixture was evaporated
to dryness and then dissolved in EtOAc (25 mL). The solution was
quenched with aqueous HCl (10 mL), washed with a sat. aqueous so-
lution of NaHCO3 (5 mL), water, and brine, and dried (MgSO4). Evapo-
ration of the filtrate and FC gave 8 (870 mg, 100%) as a colorless oil;
Rf =0.6 (PE/EtOAc 1:1); [a]25859 =+73 (c=0.183 in CHCl3); 1H NMR
ꢀ
ꢀ
ꢀ
3
3
ꢀ
ꢀ
ꢀ
ꢀ
C(6))=0.9 Hz; H-5), 4.27 (dd, J(H C(1’),H C(2’))=6.6, J(H C(1’),H
2
ꢀ
ꢀ
C(3))=2.6 Hz; H C(1’)), 4.23 (d, J=13.0 Hz; Ha C(NCH2Ph)), 4.19–
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
4.10(m, 3H; H C(6’), Ha C(7’), H C(5’)), 3.95 (d, J(H C(3’),H
2
ꢀ
ꢀ
C(4’))=4.2 Hz; H C(3’)), 3.87 (d, J=13.0 Hz; Hb C(NCH2Ph)), 3.84 (d,
2J=7.6 Hz; Hendo C(6)), 3.85–3.80 (m, 2H; H C(4’), H C(2’)), 3.74 (dd,
ꢀ
ꢀ
ꢀ
2J=7.6, 3J(Hexo C(6),H C(5))=5.8 Hz; Hexo C(6)), 3.70 (dd, 2J=12.9,
ꢀ
ꢀ
ꢀ
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J(Hb C(7’),H C(6’))=1.2 Hz; Hb C(7’)), 3.45 (d, J(H C(2),H C(3))=
9.83 Hz; H C(2)), 3.25 (m, 4H; H C(3),3H C(OCH3)), 0.96, 0.93, 0.92,
ꢀ
ꢀ
ꢀ
ꢀ
0.87 (4ꢃs, 36H; 36ꢃH C(SiC(CH3)3)), 0.14, 0.13, 0.13, 0.12, 0.11, 0.10,
0.10, 0.09 ppm (8ꢃs, 24H; 24ꢃH C(SiCH3)); 13C NMR (100.6 MHz,
ꢀ
CDCl3): d=214.0 (s; C(4)), 137.0 (s; C(arom)), 129.8 (d, 1J(C,H)=
159 Hz; C(arom)), 128.1 (d, 1J(C,H)=156 Hz; C(arom)), 127.3 (d,
1J(C,H)=159 Hz; C(arom)), 100.3 (d, 1J(C,H)=179 Hz; C(1)), 79.5 (d,
1J(C,H)=146 Hz; C(2’)), 78.4 (d, 1J(C,H)=159 Hz; C(5)), 73.3 (d,
1J(C,H)=154, C4’), 70.2 (d, 1J(C,H)=141 Hz; C(3’)), 67.4 (d, 1J(C,H)=
144 Hz; C(1’)), 70.4 (d, 1J(C,H)=146 Hz; C(5’)), 67.0 (t, 1J(C,H)=
154 Hz; C(6)), 66.7 (d, 1J(C,H)=147 Hz; C(6’)), 64.9 (d, 1J(C,H)=
126 Hz; C(2)), 62.0 (q, 1J(C,H)=125 Hz; C(OCH3)), 58.5 (t, 1J(C,H)=
143 Hz; C(7’)), 46.3 (d, 1J(C,H)=143 Hz; C(3)), 25.9, 25.89, 25.85, 25.7
(4ꢃq, 1J(C,H)=125 Hz; (CH3)3CSi), 18.2, 18.1, 17.9, 17.0 (4ꢃs;
(CH3)3CSi), ꢀ4.4, ꢀ4.6, ꢀ4.7, ꢀ4.9, ꢀ5.0, ꢀ5.1, ꢀ5.3, ꢀ5.5 ppm (8ꢃq,
1J(C,H)=118 Hz, CH3Si); IR (film): n˜ =3550, 2954, 2857, 1718, 1471,
1263, 1129, 880, 777, 741 cmꢀ1; HRMS (MALDI-TOF): m/z: calcd for
C45H85NO10Si4Na+: 934.5148; found: 934.5134; elemental analysis calcd
(%) for C45H85NO10Si4 (912.50): C 59.23, H 9.39, N 1.53; found: C 59.33,
H 9.33, N 1.55.
ꢀ
(400 MHz, CDCl3): d=7.47–7.42 (m, 2H; H C(arom)), 7.33–7.22 (m,
6H; H C(arom)), 5.87–5.77 (m, 3H; H C(1’), H C(1), H C(4)), 5.33
(dd, J(H C(6’),H C(5’))=6.2, J(H C(6’),Ha C(7’))=3.1 Hz; H C(6’)),
ꢀ
ꢀ
ꢀ
ꢀ
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5.25 (dd, J(H C(3’),H C(4’))=4.0, J(H C(3’),H C(2’))=3.7 Hz; H
3
3
ꢀ
ꢀ
ꢀ
ꢀ
C(3’)), 4.84 (dd, J(H C(4’),H C(3’))=4.0, J(H C(4’),H C(5’))=
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1.2 Hz; H C(4’)), 4.72 (dd, J(H C(5),H C(4))=7.7, J(H C(5),Hexo
C(6))=4.6 Hz; H C(5)), 4.68 (d, J=12.9 Hz; Ha C(7’)), 4.29–4.20 (m,
2
ꢀ
ꢀ
2
ꢀ
ꢀ
ꢀ
ꢀ
3H; Hb C(7’), H C(2’), H C(5’)), 4.02 (d, J=12.9 Hz; Ha C(NCH2Ph);
2
3.95 (d, 2J=7.4 Hz; Hendo C(6)), 3.79 (d, J=12.9 Hz; Hb C(NCH2Ph);
ꢀ
ꢀ
2
3
ꢀ
ꢀ
ꢀ
3.42 (dd, J=7.4, J(Hexo C(6),H C(5))=4.6 Hz; Hexo C(6)), 3.20 (s, 3H;
H C(OCH3)), 2.72 (m; H C(2)), 5.31 (ddd, J(H C(3),H C(2))=10.8,
J(H C(3),H C(4))=5.5, J(H C(3),H C(1’))=2.6 Hz; H C(3)), 2.13–
3
ꢀ
ꢀ
ꢀ
ꢀ
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1.87 ppm (6ꢃs, 18H; H C(CH3COO)); 13C NMR (100.6 MHz, CDCl3):
d=170.7, 170.1, 169.8, 169.4, 169.2, 168.8 (6ꢃs; C(CH3COO)), 137.3 (s;
C(arom)), 129.9 (d, 1J(C,H)=159 Hz; C(arom)), 128.0 (d, 1J(C,H)=
156 Hz; C(arom)), 127.2 (d, 1J(C,H)=156 Hz; C(arom)), 99.3 (d,
1J(C,H)=179 Hz; C(1)), 71.9 (d, 1J(C,H)=159 Hz; C(5)), 71.7 (d,
1J(C,H)=146 Hz; C(2’)), 67.3 (d, 1J(C,H)=144 Hz; C(1’)), 67.1 (d,
1J(C,H)=154 Hz; C(4’)), 66.6 (d, 1J(C,H)=141 Hz; C(3’)), 66.3 (d,
1J(C,H)=144 Hz; C(4)), 65.5 (d, 1J(C,H)=147 Hz; C(6’)), 65.4 (d,
1J(C,H)=146 Hz; C(5’)), 64.5 (d, 1J(C,H)=143 Hz; C(2)), 62.6 (t,
1J(C,H)=154 Hz; C(6)), 62.3 (q, 1J(C,H)=122 Hz; OCH3), 59.2 (t, 1J-
ꢀ
1,6-Anhydro-3-{(1R)-2,6-anhydro-3,4,5,7-tetra-O-[(tert-butyl)dimethylsil-
yl]-d-glycero-l-manno-heptitol-1-C-yl}-2-[(N-benzyl-N-methoxy)amino]-
2,3-dideoxy-b-d-galacto-hexopyranose (7): A solution of LiBH4 in THF
(7.0 mL, 14.0 mmol) was added dropwise at ꢀ788C to a solution of 6
(3.50 mg, 3.84 mmol) in THF (50 mL). The mixture was stirred at ꢀ788C
to 158C for 4 h. An aqueous NH4Cl solution (25 mL) was added. The re-
action mixture was warmed to 208C. An aqueous solution of sodium po-
tassium tartrate (25 mL) was added. The aqueous phase was extracted
with CH2Cl2 (100 mL; three times). The combined organic phases were
dried and concentrated in vacuo. FC (4:1, light petroleum ether/Et2O)
gave 7 (3.22 g, 92%) as a colorless oil; Rf =0.32 (PE/diethyl ether 7:3);
[a]2D5 =+26 (c=0.275 in CHCl3); 1H NMR (400 MHz, CDCl3): d=7.45–
(C,H)=143 Hz; C(7’)), 59.2 (t, 1J(C,H)=145 Hz; C(NCH2Ph)), 33.0 (d,
1
1J(C,H)=126 Hz; C(3)), 21.0–20.5 ppm (6ꢃq, J(C,H)=130 Hz; H C-
ꢀ
(CH3COO)); IR (film): n˜ =2058, 2983, 2897, 1751, 1665, 1431, 1370, 735,
701 cmꢀ1; HRMS (MALDI-TOF): calcd for C33H43NO16Na+: 732.2479;
found: 732.2469.
ꢀ
7.39 (m, 2H; ArH); 7.38–7.27 (m, 3H; ArH), 5.84 (s; H C(1)), 4.84 (m;
3
3
ꢀ
ꢀ
ꢀ
ꢀ
H C(4)), 4.54 (dd, J(H-5,H C(4))=7.0, J(H C(5),Hexo C(6))=5.4 Hz;
H C(5)), 4.43 (dd, 2J=11.5, J(Ha C(7’),H C(6’))=9.9 Hz; Ha C(7’)),
4,6-Di-O-acetyl-3-C-[(1R)-2,6-anhydro-1,3,4,5,7-penta-O-acetyl-d-glyc-
ero-l-manno-heptitol-1-C-yl]-2-[(N-benzyl-N-methoxy)amino]-2,3-di-
deoxy-b-d-galacto-hexopyranosyl phenylsulfide (9b): A mixture of
3
ꢀ
ꢀ
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
ꢀ
4.37–4.30 (m, 2H; Hendo C(6), H C(1’)), 4.27 (dd, J(H C(5’),H C(6’))=
3
3
ꢀ
ꢀ
ꢀ
6.4, J(H C(5’),HC-(4’))=2.6 Hz; H C(5’)), 4.13 (d, J(H C(2’),H-(1’))=
8
2
ꢀ
ꢀ
9.3 Hz; H C(2’)), 3.64 (d, J=13.1 Hz; Ha C(NCH2Ph)), 3.98–3.89 (m,
(0.316 g, 0.450 mmol), (phenylthio)trimethylsilane (0.254 mL,
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3H; H C(3’), H C(6’), Hb C(NCH2Ph)), 3.72 (dd, J(H C(4’),H
1.345 mmol), and ZnI2 (0.42 g, 1.333 mmol) in dry CH2Cl2 (7 mL) was
stirred at 208C for 2 h. The mixture was diluted with CH2Cl2 (50 mL) and
washed successively with sat. aqueous NaHCO3 (30 mL), water (20 mL,
three times), and brine (20 mL), dried (MgSO4), and evaporated. The
residue was dissolved in THF (10 mL), TBAF (0.450 mL, 0.450 mmol)
was added, and the mixture was stirred at 208C for 1 h. The solvent was
C(3’))=3.5, J(H C(4’),H C(5’))=2.6 Hz; H C(4’)), 3.80 (dd, 2J=11.5,
3
ꢀ
ꢀ
ꢀ
J(Hb C(7’),H C(6’))=1.9 Hz; Hb C(7’)), 3.51 (dd, 2J=7.4, 3J(H-5,Hexo
3
ꢀ
ꢀ
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
C(6))=5.4 Hz; Hexo C(6)), 3.3 (s, 3H; H C(OCH3)), 4.24 (d, J(H
C(2),H C(3))=9.6 Hz; H C(2)), 2.64 (ddd, 3J(H-3,H-2)=9.6, 3J(H-3,H-
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
4)=6.7, J(H C(3), H C(1’))=2.6 Hz; H C(3)), 0.98, 0.95, 0.94, 0.93 (4ꢃ
Chem. Eur. J. 2005, 11, 3565 – 3573
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3569