l-chiro-Inositol Derivatives from myo-Inositol. Building Blocks for Inositol­phosphoglycans

Abstract

A straightforward synthesis of l-chiro-inositol, deoxy l-chiro-inositol derivatives and l-chiro-inositol building blocks for the preparation of inositolphosphoglycans, is reported from myo-inositol. Glycosylation with 2-azido-3,4,6-tri-O-benzyl-2-deoxy-d-glucopyranosyl trichloroacetimidate gave the corresponding pseudodisaccharide derivatives.

carbocycles - isomerization - natural products - glyco­sylation - oligosaccharides

References

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(-)2-Deoxy-scyllo-inosose (5). To a solution of 3,4,5,6-tetra-O-benzyl-1-O-trifluoromethanesulfonyl-l-myo-inositol (4, 105 mg, 0.156 mmol), in a mixture of dry toluene and DMF (1/1, 5 mL), cesium trifluoracetate (192 mg, 0.781 mmol) and a catalytic amount of DMAP, were added. After 48 h at room temperature, the resulting slurry was diluted with EtOAc, washed with water, brine, dried over Na₂SO₄ and concentrated. The solvent was evaporated and the residue purified by flash chromatography (hexane/EtOAc, 4:1), to give 81 mg (0.155 mmol, 100%). [α]_D -22.0° (c= 0.5, CHCl₃). Anal. Calcd. for C₃₄H₃₄O₅: C, 78.13%; H, 6.55%; found : C, 77.70%; H, 6.66%.

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2-Amino-2-deoxy- d -glucopyranosyl-α(1→1)- l - chiro -inositol (IIa): ¹H NMR (500 MHz, D₂O): δ = 5.08 (d, 1 H, J = 3.65 Hz, H_{1 ′}); 4.13 (t, 1 H, J = 3.81 Hz, H₁); 4.0 (t, 1 H, J = 3.51 Hz, H₆); 3.88-3.85 (m, 2 H, H_{6 ′a} and H₅); 3.79-3.71 (m, 3 H, H_{6 ′b}, H₄ and H₂); 3.65 (m, 1 H, H_{5 ′}); 3.58 (t, 1 H, J = 9.61 Hz, H₃); 3.53 (t, 1 H, J = 9.61 Hz, H_{3 ′}); 3.38 (t, 1 H, J = 9.31 Hz, H_{4 ′}) and 2.73 (dd, 1 H, J = 10.4 Hz, 3.51 Hz, H_{2 ′}). FAB HRMS calcd for C₁₂H₂₃NO₁₀ + Na⁺: 364.1219, found 364.1209. 2-Amino-2-deoxy- d -glucopyranosyl-β(1→1)-l- chiro -inositol (IIb): ¹H NMR (500 MHz, D₂O):
δ = 4.43 (d, 1 H, J = 8.24 Hz, H_{1 ′}); 4.17 (t, 1 H, J = 3.66 Hz, H₁); 4.14 (t, 1 H, J = 3.60 Hz, H₆); 3.88-3.68 (m, 6 H, 2H_{6 ′}, H₂, H₅, H₃ and H₄); 3.46 (m, 1 H, H_{5 ′}); 3.40 (t, 1 H, J = 8.85 Hz, H_{4 ′}); 3.36 (t, 1 H, J = 9.31 Hz, H_{3 ′}) and 2.69 (dd, 1 H,
J = 9.30 Hz, 8.24 Hz, H_{2 ′}). FAB HRMS calcd for C₁₂H₂₃NO₁₀ + Na⁺: 364.1219, found 364.1223.