(3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture that consists of 42.1 g (100 mmol) of 2,3,4,6-tetra-O-benzyl-galactopyranose, 1.7 g (5 mmol) of tetrabutylammonium hydrogen sulfate and 33.7 g (600 mmol) of fine-powder potassium hydroxide in 350 ml of diethoxymethane is cooled to 10° C. At 10° C., 40.2 g (150 mmol) of N-(3-bromopropyl)-phthalimide, dissolved in 100 ml of 1,2-dimethoxyethane, is added in drops over 40 minutes while being stirred vigorously. It is stirred for three hours at 10° C. 300 ml of benzene is added, solid is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The filtrate residue is dissolved in 500 ml of ethanol, 25.03 ml of hydrazine hydrate (500 mmol) is added, and it is refluxed for six hours. It is allowed to cool to 0° C., deposited precipitate is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The residue is dissolved in 400 ml of dichloromethane, this solution is washed twice with 5% aqueous sodium hydroxide solution, then once with water (in each case 300 ml). The organic phase is evaporated to the dry state in a vacuum, and the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1). is added in drops over 40 minutes It is stirred for three hours at 10° C solid is filtered out the filtrate is evaporated to the dry state in a vacuum The filtrate residue is dissolved in 500 ml of ethanol it is refluxed for six hours to cool to 0° C. is filtered out the filtrate is evaporated to the dry state in a vacuum The residue is dissolved in 400 ml of dichloromethane this solution is washed twice with 5% aqueous sodium hydroxide solution The organic phase is evaporated to the dry state in a vacuum the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3,4,6-Tetra-O-benzyl-D-galactopyranose (107 g) was dissolved in ethanol (0.6 L) and, whilst stirring at 0° C., sodium borohydride (31 g) was added. After stirring overnight TLC analysis indicated completion of the reaction. The ethanol solution was partitioned between water (3 L) and ether (1.5 L). The organic phase was dried (Na2SO4), filtered and concentrated. The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) and then crystallised from a mixture of ethyl acetate/petroleum ether to give 2,3,4,6-tetra-O-benzyl-D-galactitol (97 g, 91%) as a white solid. 1H NMR (CDCl3): δ 2.4 (1H, bs), 3.35 (1H, bs), 3.55 (2H, m), 3.8 (3H, m), 3.9 (2H, m), 4.1 (1H, m), 4.4-4.8 (8H, m, OCH2Ph), 7.2-7.4 (20H, m, ArH). Mass spectrum: m/z 543 (M+H)+ 565 (M+Na)+. After stirring overnight TLC analysis completion of the reaction The ethanol solution was partitioned between water (3 L) and ether (1.5 L) The organic phase was dried (Na2SO4) filtered concentrated The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) crystallised from a mixture of ethyl acetate/petroleum ether

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3,4,6-Tetra-O-benzyl-D-galactopyranose (107 g) was dissolved in ethanol (0.6 L) and, whilst stirring at 0° C., sodium borohydride (31 g) was added. After stirring overnight TLC analysis indicated completion of the reaction. The ethanol solution was partitioned between water (3 L) and ether (1.5 L). The organic phase was dried (Na2SO4), filtered and concentrated. The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) and then crystallised from a mixture of ethyl acetate/petroleum ether to give 2,3,4,6-tetra-O-benzyl-D-galactitol (97 g, 91%) as a white solid. 1H NMR (CDCl3): δ 2.4 (1H, bs), 3.35 (1H, bs), 3.55 (2H, m), 3.8 (3H, m), 3.9 (2H, m), 4.1 (1H, m), 4.4-4.8 (8H, m, OCH2Ph), 7.2-7.4 (20H, m, ArH). Mass spectrum: m/z 543 (M+H)+ 565 (M+Na)+. After stirring overnight TLC analysis completion of the reaction The ethanol solution was partitioned between water (3 L) and ether (1.5 L) The organic phase was dried (Na2SO4) filtered concentrated The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) crystallised from a mixture of ethyl acetate/petroleum ether

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trimethylsilyl bromide (7.96 g, 6.78 ml. 52 mmol) was added with a syringe to a mixture of 2,3,4,6-tetra-O-benzyl-D-galactopyranose (28 g, 52 mmol), 2-bromoethanol (4.46 ml, 40.0 mmol), cobalt(II)bromide (11.4 g, 52.0 mmol), tetraethylammonium bromide (10.9 g, 52.0 mmol) and molecular sieves (4 Å, 41 g) in 138 ml of methylene chloride under nitrogen with protection from light. (The cobalt(II)chloride had been dried at 180°, 5×10-3 mm Hg over night. ) The reaction mixture was stirred at room temperature over night and filtered. The residue was washed with 100 ml of methylene chloride. The filtrate was evaporated at reduced pressure to give 25.8 g of the crude product, which was chromatographed (SiO2, isooctane:ethyl acetate 3:2) Fraction 1 was the pure title compound (6.0 g) and fraction 2 was a mixture of the anomers (α/β, 10.0 g) Total yield of glycosides 16 g (48 %) (This procedure is a slight modification of that of Koto et al.34.) [α]D23 =+30.5° (c 1.4, CHCl3). 1H-NMR (CDCl3, TMS) δ 7.30 (m, 20H, Ph), 4.97-4.42 (m, 9H), 4.0-3.8 (m, 6H), 3.52 (t, 4H, inter alia CH2Br). 13C-NMR (CDCl, TMS) δ 103.3 (d, Cl, JC--H =168 Hz), 84.2, 81.6, 80.2, 75.0 (C2-C5), 80.0, 78.7, 78.6, 78.5, 74.2, 73.5 (C6, benzylic CH2 and aglycon O--CH2), 35.5 (CH2Br) (The cobalt(II)chloride had been dried at 180° 5×10-3 mm Hg over night filtered The residue was washed with 100 ml of methylene chloride The filtrate was evaporated at reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trimethylsilyl bromide (7.96 g, 6.78 ml. 52 mmol) was added with a syringe to a mixture of 2,3,4,6-tetra-O-benzyl-D-galactopyranose (28 g, 52 mmol), 2-bromoethanol (4.46 ml, 40.0 mmol), cobalt(II)bromide (11.4 g, 52.0 mmol), tetraethylammonium bromide (10.9 g, 52.0 mmol) and molecular sieves (4 Å, 41 g) in 138 ml of methylene chloride under nitrogen with protection from light. (The cobalt(II)chloride had been dried at 180°, 5×10-3 mm Hg over night. ) The reaction mixture was stirred at room temperature over night and filtered. The residue was washed with 100 ml of methylene chloride. The filtrate was evaporated at reduced pressure to give 25.8 g of the crude product, which was chromatographed (SiO2, isooctane:ethyl acetate 3:2) Fraction 1 was the pure title compound (6.0 g) and fraction 2 was a mixture of the anomers (α/β, 10.0 g) Total yield of glycosides 16 g (48 %) (This procedure is a slight modification of that of Koto et al.34.) [α]D23 =+30.5° (c 1.4, CHCl3). 1H-NMR (CDCl3, TMS) δ 7.30 (m, 20H, Ph), 4.97-4.42 (m, 9H), 4.0-3.8 (m, 6H), 3.52 (t, 4H, inter alia CH2Br). 13C-NMR (CDCl, TMS) δ 103.3 (d, Cl, JC--H =168 Hz), 84.2, 81.6, 80.2, 75.0 (C2-C5), 80.0, 78.7, 78.6, 78.5, 74.2, 73.5 (C6, benzylic CH2 and aglycon O--CH2), 35.5 (CH2Br) (The cobalt(II)chloride had been dried at 180° 5×10-3 mm Hg over night filtered The residue was washed with 100 ml of methylene chloride The filtrate was evaporated at reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3,4,6-Tetra-O-benzyl-D-galactopyranose (107 g) was dissolved in ethanol (0.6 L) and, whilst stiffing at 0° C., sodium borohydride (31 g) was added. After stiffing overnight TLC analysis indicated completion of the reaction. The ethanol solution was partitioned between water (3 L) and ether (1.5 L). The organic phase was dried (Na2SO4), filtered and concentrated. The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) and then crystallised from a mixture of ethyl acetate/petroleum ether to give 2,3,4,6-tetra-O-benzyl-D-galactitol (97 g, 91%) as a white solid. 1H NMR (CDCl3): δ 2.4 (1H, bs), 3.35 (1H, bs), 3.55 (2H, m), 3.8 (3H, m), 3.9 (2H, m), 4.1 (1H, m), 4.4-4.8 (8H, m, OCH2Ph), 7.2-7.4 (20H, m, ArH). Mass spectrum: m/z 543 (M+H)+565 (M+Na)+. whilst stiffing at 0° C. completion of the reaction The ethanol solution was partitioned between water (3 L) and ether (1.5 L) The organic phase was dried (Na2SO4) filtered concentrated The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) crystallised from a mixture of ethyl acetate/petroleum ether

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture that consists of 42.1 g (100 mmol) of 2,3,4,6-tetra-O-benzyl-galactopyranose, 1.7 g (5 mmol) of tetrabutylammonium hydrogen sulfate and 33.7 g (600 mmol) of fine-powder potassium hydroxide in 350 ml of benzene is cooled to 10° C. At 10° C., 40.2 g (150 mmol) of N-(3-bromopropyl)-phthalimide, dissolved in 100 ml of benzene, is added in drops over 40 minutes while being stirred vigorously. It is stirred for three hours at 10° C. 300 ml of benzene is added, solid is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The filtrate residue is dissolved in 500 ml of ethanol, 25.03 ml of hydrazine hydrate (500 mmol) is added, and it is refluxed for six hours. It is allowed to cool to 0° C., deposited precipitate is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The residue is dissolved in 400 ml of dichloromethane, this solution is washed twice with 5% aqueous sodium hydroxide solution, then once with water (in each case 300 ml). The organic phase is evaporated to the dry state in a vacuum, and the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1). is added in drops over 40 minutes It is stirred for three hours at 10° C solid is filtered out the filtrate is evaporated to the dry state in a vacuum The filtrate residue is dissolved in 500 ml of ethanol it is refluxed for six hours to cool to 0° C. is filtered out the filtrate is evaporated to the dry state in a vacuum The residue is dissolved in 400 ml of dichloromethane this solution is washed twice with 5% aqueous sodium hydroxide solution The organic phase is evaporated to the dry state in a vacuum the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1)

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture that consists of 42.1 g (100 mmol) of 2,3,4,6-tetra-O-benzyl-galactopyranose, 1.7 g (5 mmol) of tetrabutylammonium hydrogen sulfate and 33.7 g (600 mmol) of fine-powder potassium hydroxide in 350 ml of diethoxymethane is cooled to 10° C. At 10° C., 40.2 g (150 mmol) of N-(3-bromopropyl)-phthalimide, dissolved in 100 ml of 1,2-dimethoxyethane, is added in drops over 40 minutes while being stirred vigorously. It is stirred for three hours at 10° C. 300 ml of benzene is added, solid is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The filtrate residue is dissolved in 500 ml of ethanol, 25.03 ml of hydrazine hydrate (500 mmol) is added, and it is refluxed for six hours. It is allowed to cool to 0° C., deposited precipitate is filtered out, and the filtrate is evaporated to the dry state in a vacuum. The residue is dissolved in 400 ml of dichloromethane, this solution is washed twice with 5% aqueous sodium hydroxide solution, then once with water (in each case 300 ml). The organic phase is evaporated to the dry state in a vacuum, and the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1). is added in drops over 40 minutes It is stirred for three hours at 10° C solid is filtered out the filtrate is evaporated to the dry state in a vacuum The filtrate residue is dissolved in 500 ml of ethanol it is refluxed for six hours to cool to 0° C. is filtered out the filtrate is evaporated to the dry state in a vacuum The residue is dissolved in 400 ml of dichloromethane this solution is washed twice with 5% aqueous sodium hydroxide solution The organic phase is evaporated to the dry state in a vacuum the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3,4,6-Tetra-O-benzyl-D-galactopyranose (107 g) was dissolved in ethanol (0.6 L) and, whilst stirring at 0° C., sodium borohydride (31 g) was added. After stirring overnight TLC analysis indicated completion of the reaction. The ethanol solution was partitioned between water (3 L) and ether (1.5 L). The organic phase was dried (Na2SO4), filtered and concentrated. The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) and then crystallised from a mixture of ethyl acetate/petroleum ether to give 2,3,4,6-tetra-O-benzyl-D-galactitol (97 g, 91%) as a white solid. 1H NMR (CDCl3): δ 2.4 (1H, bs), 3.35 (1H, bs), 3.55 (2H, m), 3.8 (3H, m), 3.9 (2H, m), 4.1 (1H, m), 4.4-4.8 (8H, m, OCH2Ph), 7.2-7.4 (20H, m, ArH). Mass spectrum: m/z 543 (M+H)+ 565 (M+Na)+. After stirring overnight TLC analysis completion of the reaction The ethanol solution was partitioned between water (3 L) and ether (1.5 L) The organic phase was dried (Na2SO4) filtered concentrated The resulting oil was purified by flash chromatography (gradient elution using 20→50% ethyl acetate/petroleum ether) crystallised from a mixture of ethyl acetate/petroleum ether

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trimethylsilyl bromide (7.96 g, 6.78 ml. 52 mmol) was added with a syringe to a mixture of 2,3,4,6-tetra-O-benzyl-D-galactopyranose (28 g, 52 mmol), 2-bromoethanol (4.46 ml, 40.0 mmol), cobalt(II)bromide (11.4 g, 52.0 mmol), tetraethylammonium bromide (10.9 g, 52.0 mmol) and molecular sieves (4 Å, 41 g) in 138 ml of methylene chloride under nitrogen with protection from light. (The cobalt(II)chloride had been dried at 180°, 5×10-3 mm Hg over night. ) The reaction mixture was stirred at room temperature over night and filtered. The residue was washed with 100 ml of methylene chloride. The filtrate was evaporated at reduced pressure to give 25.8 g of the crude product, which was chromatographed (SiO2, isooctane:ethyl acetate 3:2) Fraction 1 was the pure title compound (6.0 g) and fraction 2 was a mixture of the anomers (α/β, 10.0 g) Total yield of glycosides 16 g (48 %) (This procedure is a slight modification of that of Koto et al.34.) [α]D23 =+30.5° (c 1.4, CHCl3). 1H-NMR (CDCl3, TMS) δ 7.30 (m, 20H, Ph), 4.97-4.42 (m, 9H), 4.0-3.8 (m, 6H), 3.52 (t, 4H, inter alia CH2Br). 13C-NMR (CDCl, TMS) δ 103.3 (d, Cl, JC--H =168 Hz), 84.2, 81.6, 80.2, 75.0 (C2-C5), 80.0, 78.7, 78.6, 78.5, 74.2, 73.5 (C6, benzylic CH2 and aglycon O--CH2), 35.5 (CH2Br) (The cobalt(II)chloride had been dried at 180° 5×10-3 mm Hg over night filtered The residue was washed with 100 ml of methylene chloride The filtrate was evaporated at reduced pressure