Synthesis of new mono- and disaccharidic carboxymethylglycoside lactones (CMGLs) and their use toward 1,2-bisfunctionalized carbohydrate synthons

A general and convenient access to mono- and disaccharidic carboxymethyl glycoside lactones (CMGLs) is described. By taking advantage of the free OH at the 2-position, obtained after the opening of CMGLs by amines, the synthesis of a series of new 1,2-bisfunctionalized carbohydrate synthons is reported.

Figure optionsDownload as PowerPoint slide

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosideC20H30O12Ee = 100%[α]D = +129 (c 1.00, CH2Cl2)Source of chirality: α-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosideC20H30O12Ee = 100%[α]D = −29 (c 1.00, CH2Cl2)Source of chirality: β-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-d-mannopyranosideC20H30O12Ee = 100%[α]D = +46 (c 1.00, CH2Cl2)Source of chirality: β-d-mannopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-mannopyranosideC20H30O12Ee = 100%[α]D = +57 (c 1.00, CH2Cl2)Source of chirality: α-d-mannopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-galactopyranosideC20H30O12Ee = 100%[α]D = +110 (c 0.50, CH2Cl2)Source of chirality: α-d-galactopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosideC20H30O12Ee = 100%[α]D = +110 (c 1.00, CH2Cl2)Source of chirality: β-d-galactopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-α-l-fucopyranosideC18H28O10Ee = 100%[α]D = −103 (c 3.00, CH2Cl2)Source of chirality: α-l-fucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-l-fucopyranosideC18H28O10Ee = 100%[α]D = +10 (c 2.00, CH2Cl2)Source of chirality: β-l-fucopyranoside

(tert-Butyloxycarbonyl)methyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-d-glucopyranosideC20H31NO11Ee = 100%[α]D = +73 (c 1.00, CH2Cl2)Source of chirality: 2-amino-2-deoxy-2-N-acetyl-α-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-d-glucopyranosideC32H46O20Ee = 100%[α]D = +30 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-d-glucopyranosideC32H46O20Ee = 100%[α]D = +5 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-β-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-d-glucopyranosideC32H46O20Ee = 100%[α]D = +43 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-d-glucopyranosideC32H46O20Ee = 100%[α]D = +69 (c 0.5, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(tert-Butyloxycarbonyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-d-glucopyranosideC32H46O20Ee = 100%[α]D = +59 (c 0.3, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-β-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-mannopyranosideC16H22O12Ee = 100%[α]D = −47 (c 1.00, CH2Cl2)Source of chirality: β-d-mannopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-α-l-fucopyranosideC14H20O10Ee = 100%[α]D = −135 (c 1.00, CH2Cl2)Source of chirality: α-l-fucopyranoside

Carboxymethyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-d-glucopyranosideC16H23NO11Ee = 100%[α]D = +81 (c 0.50, CH2Cl2)Source of chirality: 2-amino-2-deoxy-2-N-acetyl-α-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-d-glucopyranosideC28H38O20Ee = 100%[α]D = +57 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-d-glucopyranosideC28H38O20Ee = 100%[α]D = −6 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-β-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-d-glucopyranosideC28H38O20Ee = 100%[α]D = +50 (c 0.5, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-d-glucopyranosideC28H38O20Ee = 100%[α]D = +91 (c 0.50, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-d-glucopyranosideC28H38O20Ee = 100%[α]D = +61 (c 0.3, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-β-d-glucopyranoside

Carboxymethyl-3,4,6-tri-O-acetyl-β-d-mannopyranoside-2-O-lactoneC14H18O10Ee = 100%[α]D = −55 (c 1.00, CH2Cl2)Source of chirality: β-d-mannopyranoside

Carboxymethyl-3,4-di-O-acetyl-α-l-fucopyranoside-2-O-lactoneC12H16O8Ee = 100%[α]D = −124 (c 1.00, CH2Cl2)Source of chirality: α-l-fucopyranoside

Carboxymethyl-3,4,6-tri-O-acetyl-β-l-fucopyranoside-2-O-lactoneC12H16O8Ee = 100%[α]D = −88 (c 1.00, CH2Cl2)Source of chirality: β-d-fucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-3,6-di-O-acetyl-α-d-glucopyranoside-2-O-lactoneC26H34O18Ee = 100%[α]D = +68 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl-(1→4)-3,6-di-O-acetyl-β-d-glucopyranoside-2-O-lactoneC26H34O18Ee = 100%[α]D = +5 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-β-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-3,6-di-O-acetyl-α-d-glucopyranoside-2-O-lactoneC26H34O18Ee = 100%[α]D = +109 (c 1.00, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

Carboxymethyl2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-3,6-di-O-acetyl-β-d-glucopyranoside-2-O-lactoneC26H34O18Ee = 100%[α]D = +54 (c 0.3, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-β-d-glucopyranoside

Carboxymethyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl-(1→4)-3,6-di-O-acetyl-α-d-glucopyranoside-2-O-lactoneC26H34O18Ee = 100%[α]D = +44 (c 1.00, CH2Cl2)Source of chirality: O-(β-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(N-Allylcarbamoyl)methyl 3,4,6-tri-O-acetyl-α-d-glucopyranosideC17H25NO10Ee = 100%[α]D = +118 (c 1.00, CH2Cl2)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 2-O-propylcarbamoyl-α-d-glucopyranosideC25H24N2O8Ee = 100%[α]D = +11 (c 0.3, CH3OH)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-hexadecylcarbamoyl-α-d-glucopyranosideC34H56N2O11Ee = 100%[α]D = +78 (c 1.00, CH2Cl2)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 2-O-hexadecylcarbamoyl-α-d-glucopyranosideC28H50N2O8Ee = 100%[α]D = +43(c 0.50, CH3OH)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-carbamoyl-α-d-glucopyranosideC18H24N2O11Ee = 100%[α]D = +98 (c 1.00, CH2Cl2)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 2-O-carbamoyl-α-d-glucopyranosideC12H18N2O8Ee = 100%[α]D = +32 (c 0.5, CH3OH2)Source of chirality: α-d-glucopyranoside

(N-Allylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-carbamoyl-α-d-glucopyranosideC18H20N2O11Ee = 100%[α]D = +107 (c 1.00, CH2Cl2)Source of chirality: α-d-glucopyranoside

(N-Allylcarbamoyl)methyl 2-O-carbamoyl-α-d-glucopyranosideC12H20N2O8Ee = 100%[α]D = +51 (c 0.5, CH3OH)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-3,6-di-O-acetyl-α-d-glucopyranosideC29H39N4O18Ee = 100%[α]D = +107 (c 0.3, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-3,6-di-O-acetyl-2-O-hexadecylcarbamoyl-α-d-glucopyranosideC46H72N2O19Ee = 100%[α]D = +77 (c 0.5, CH2Cl2)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl α-d-glucopyranosyl-(1→4)-2-O-hexadecylcarbamoyl-α-d-glucopyranosideC34H60N2O13Ee = 100%[α]D = +57 (c 0.5, CH3OH)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl-(1→4)-3,6-di-O-acetyl-2-O-carbamoyl-α-d-glucopyranosideC30H40N2O19Ee = 100%[α]D = +61 (c 1.00, CH2Cl2)Source of chirality: α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl α-d-glucopyranosyl-(1→4)-2-O-carbamoyl-α-d-glucopyranosideC18H28N2O13Ee = 100%[α]D = +11 (c 0.3, CH2Cl2)Source of chirality: α-d-glucopyranoside

N-methyl[-4-[1-(5′-deoxyuridin)-1,2,3-triazole]]-carboxymethyl-2-O-carbamoyl-α-d-glucopyranosideC21H29N7O13Ee = 100%[α]D = +50 (c 0.3, H2O)Source of chirality: α-d-glucopyranoside

N-methyl[-4-[1-(5′-deoxyuridin)-1,2,3-triazole]]-carboxymethyl α-d-glucopyranosyl-(1→4)-2-O-carbamoyl-α-d-glucopyranosideC27H39N7O18Ee = 100%[α]D = +105 (c 0.3, CH3OH)Source of chirality: O-(α-d-glucopyranosyl)-(1→4)-α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-[(tert-butyloxycarbonyl)methyl]-α-d-glucopyranosideC23H33NO12Ee = 100%[α]D = +75 (c 0.5, CH2Cl2)Source of chirality:α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-[(carboxy)methyl]-α-d-glucopyranosideC19H25NO12Ee = 100%[α]D = +58 (c 0.3, CH2Cl2)Source of chirality:α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-(propargyl)-α-d-glucopyranosideC20H25N2O10Ee = 100%[α]D = +36 (c 0.3, CH2Cl2)Source of chirality:α-d-glucopyranoside

(N-Allylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-O-(propargyl)-α-d-glucopyranosideC20H27NO10Ee = 100%[α]D = +36 (c 0.3, CH2Cl2)Source of chirality:α-d-glucopyranoside

(N-Propargylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-d-mannopyranosideC17H22N4O9Ee = 100%[α]D = +27 (c 0.3, CH2Cl2)Source of chirality:α-d-glucopyranoside

(N-Allylcarbamoyl)methyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-d-mannopyranosideC17H24N4O9Ee = 100%[α]D = +68 (c 0.5, CH2Cl2)Source of chirality: α-d-glucopyranoside