[(2R,3S,4S,5R,6S)-3,4,5,6-tetraacetyloxyoxan-2-yl]methyl acetate

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

Procedure: The synthesis of compound 9 is illustrated in FIG. 6. 20 g (51.24 mmol) of β-D-galactosepentaacetate 1 was dissolved in 150 ml THF and 6.7 ml (61.49 mmol) of benzylamine was added with a dropping funnel. The reaction was stirred for 18 h at room temperature to give 2,3,4,6-tetra-O-acetyl-β-D-galactopyranose 2.

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

Procedure: The synthesis of compounds 26-31 are depicted in FIGS. 19A and 19B and are set forth in the examples hereinbelow. In this figure, the synthesis of compounds 26, 27, 28, and 36 parallels that of compounds 17, 18, 19, and 20 as set forth above and illustrated in FIG. 18. In this regard, benzyl 4,6-O-benzylidene-2-O-benzoyl-3-O-chloroacetyl-β-D-thiogalactopyranoside (compound 31) has been produced without the necessity of chromatography. D-Galactose pentaacetate 26 is produced by slurring D-galactose and about an equimolar amount (e.g., about 1.1 equivalents) of sodium acetate (NaOAc) in dichloroethane (DCE), heating to reflux and adding at least 5 equivalents of acetic anhydride (AcOAc) dropwise to the refluxing solution (about 80°-85° C.) and then maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours) to result in formation of compound 26. This procedure optimizes the yield of β-D-galactose pentaacetate 26 and controls the exotherm of heretofore known procedures. to reflux maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours)

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

Procedure: The synthesis of compounds 26-31 are depicted in FIGS. 19A and 19B and are set forth in the examples hereinbelow. In this figure, the synthesis of compounds 26, 27, 28, and 36 parallels that of compounds 17, 18, 19, and 20 as set forth above and illustrated in FIG. 18. In this regard, benzyl 4,6-O-benzylidene-2-O-benzoyl-3-O-chloroacetyl-β-D-thiogalactopyranoside (compound 31) has been produced without the necessity of chromatography. D-Galactose pentaacetate 26 is produced by slurring D-galactose and about an equimolar amount (e.g., about 1.1 equivalents) of sodium acetate (NaOAc) in dichloroethane (DCE), heating to reflux and adding at least 5 equivalents of acetic anhydride (AcOAc) dropwise to the refluxing solution (about 80°-85° C.) and then maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours) to result in formation of compound 26. This procedure optimizes the yield of β-D-galactose pentaacetate 26 and controls the exotherm of heretofore known procedures. to reflux maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours)

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

Procedure: The synthesis of compounds 26-31 are depicted in FIGS. 3A and 3B and are set forth in the examples hereinbelow. In this figure, the synthesis of compounds 26, 27, 28, and 36 parallels that of compounds 17, 18, 19, and 20 as set forth above and illustrated in FIG. 2. In this regard, benzyl 4,6-O-benzylidene-2-O-benzoyl-3-O-chloroacetyl-β-D-thiogalactopyranoside (compound 31) has been produced without the necessity of chromatography. D-Galactose pentaacetate 26 is produced by slurring D-galactose and about an equimolar amount (e.g., about 1.1 equivalents) of sodium acetate (NaOAc) in dichloroethane (DCE), heating to reflux and adding at least 5 equivalents of acetic anhydride (AcOAc) dropwise to the refluxing solution (about 80°-85° C.) and then maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours) to result in formation of compound 26. This procedure optimizes the yield of β-D-galactose pentaacetate 26 and controls the exotherm of heretofore known procedures. to reflux maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours)

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

Procedure: The synthesis of compounds 26-31 are depicted in FIGS. 3A and 3B and are set forth in the examples hereinbelow. In this figure, the synthesis of compounds 26, 27, 28, and 36 parallels that of compounds 17, 18, 19, and 20 as set forth above and illustrated in FIG. 2. In this regard, benzyl 4,6-O-benzylidene-2-O-benzoyl-3-O-chloroacetyl-β-D-thiogalactopyranoside (compound 31) has been produced without the necessity of chromatography. D-Galactose pentaacetate 26 is produced by slurring D-galactose and about an equimolar amount (e.g., about 1.1 equivalents) of sodium acetate (NaOAc) in dichloroethane (DCE), heating to reflux and adding at least 5 equivalents of acetic anhydride (AcOAc) dropwise to the refluxing solution (about 80°-85° C.) and then maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours) to result in formation of compound 26. This procedure optimizes the yield of β-D-galactose pentaacetate 26 and controls the exotherm of heretofore known procedures. to reflux maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours)

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

Procedure: p-methoxyphenol (20.5 mmol, 2.5 g) and trimethylsilyl trifluoromethanesulfonate (0.25 mL) were added to a solution of β-D-galactose pentaacetate (5.0 g, 12.8 mmol) in anhydrous CH2Cl2 at 0° C. under nitrogen. After 4 hours at 0° C., the reaction mixture was neutralized by addition of triethylamine (1 mL) and concentrated under reduced pressure. Purification by chromatography on silica gel (ethyl acetate-petroleum ether, v/v 1:3→1.5:1) afforded 6 as an amorphous white solid in 92% yield (5.35 g). Litt22 [αD]=+9.6° (c 0.54, CHCl3); [αD]23=+3° (c 1, CHCl3); 1H NMR (500 MHz, CDCl3): δ2.01, 2.06, 2.08 and 2.19 (4 s, 3H each, 4 OAc), 3.78 (s, 3H, OMe), 4.01 (m, 1H, H-5), 4.16 (dd, 1H, J5,6b 6.5 Hz, J6a,6b 11.3 Hz, H-6b), 4.23 (dd, 1H, J5,6a 6.9 Hz, H-6a), 4.92 (d, 1H, J1,2 8.0 Hz, H-1), 5.09 (dd, 1H, J2,3 10.4 Hz, J3,4 3.3 Hz, H-3), 5.5.44-5.48 (m, 2H, H-2 and H-4), 6.80 and 6.96 (2 d, 2H each, Ph). concentrated under reduced pressure Purification by chromatography on silica gel (ethyl acetate-petroleum ether, v/v 1:3→1.5:1)

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: SnCl4 (0.6 ml) is added slowly to a solution of 2-methyl-4-nitrophenol (ref.: J. S. ANDERSON and K. C. BROWN, Synthetic Commun., 13, 233-236, 1983) and 1,2,3,4,6-penta-O-acetyl-β-D-galactose (1 g, 2.56 mmol), kept at room temperature. The reaction mixture is then stirred under nitrogen for 12 hours at 60° C. After hydrolysis in iced water, extraction with CH2Cl2, followed by washing with a saturated solution of sodium bicarbonate and then water, gives 42, which is then purified by chromatography on silica gel (yield=45%). kept at room temperature extraction with CH2Cl2 by washing with a saturated solution of sodium bicarbonate

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

Procedure: The synthesis of compound 9 is illustrated in FIG. 6. 20 g (51.24 mmol) of β-D-galactosepentaacetate 1 was dissolved in 150 ml THF and 6.7 ml (61.49 mmol) of benzylamine was added with a dropping funnel. The reaction was stirred for 18 h at room temperature to give 2,3,4,6-tetra-O-acetyl-β-D-galactopyranose 2.

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

Procedure: The synthesis of compound 9 is illustrated in FIG. 6. 20 g (51.24 mmol) of β-D-galactosepentaacetate 1 was dissolved in 150 ml THF and 6.7 ml (61.49 mmol) of benzylamine was added with a dropping funnel. The reaction was stirred for 18 h at room temperature to give 2,3,4,6-tetra-O-acetyl-β-D-galactopyranose 2.

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

Procedure: The synthesis of compounds 26-31 are depicted in FIGS. 19A and 19B and are set forth in the examples hereinbelow. In this figure, the synthesis of compounds 26, 27, 28, and 36 parallels that of compounds 17, 18, 19, and 20 as set forth above and illustrated in FIG. 18. In this regard, benzyl 4,6-O-benzylidene-2-O-benzoyl-3-O-chloroacetyl-β-D-thiogalactopyranoside (compound 31) has been produced without the necessity of chromatography. D-Galactose pentaacetate 26 is produced by slurring D-galactose and about an equimolar amount (e.g., about 1.1 equivalents) of sodium acetate (NaOAc) in dichloroethane (DCE), heating to reflux and adding at least 5 equivalents of acetic anhydride (AcOAc) dropwise to the refluxing solution (about 80°-85° C.) and then maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours) to result in formation of compound 26. This procedure optimizes the yield of β-D-galactose pentaacetate 26 and controls the exotherm of heretofore known procedures. to reflux maintaining the reaction system at this temperature for a sufficient period of time (about 16-32 hours)

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

Procedure: To a solution of 4-hydroxy-3-(2-phenylethyl)benzofuran (0.11 g) and 1,2,3,4,6-penta-O-acetyl-β-D-galactopyranose (0.37 g) in dichloromethane (5 mL) was added boron trifluoride-diethyl ether complex (0.12 mL), and the mixture was stirred at room temperature overnight. The reaction mixture was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1-3/2) to give 4-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyloxy)-3-(2-phenylethyl)benzofuran (0.13 g). This material was dissolved in methanol (5 mL). To the solution was added sodium methoxide (28% methanol solution, 0.043 mL), and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: dichloromethane/methanol=10/1) to give the title compound (24 mg). The reaction mixture was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1-3/2)

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

Procedure: To a solution of 4-hydroxy-3-(2-phenylethyl)benzofuran (0.11 g) and 1,2,3,4,6-penta-O-acetyl-β-D-galactopyranose (0.37 g) in dichloromethane (5 mL) was added boron trifluoride-diethyl ether complex (0.12 mL), and the mixture was stirred at room temperature overnight. The reaction mixture was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1-3/2) to give 4-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyloxy)-3-(2-phenylethyl)benzofuran (0.13 g). This material was dissolved in methanol (5 mL). To the solution was added sodium methoxide (28% methanol solution, 0.043 mL), and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: dichloromethane/methanol=10/1) to give the title compound (24 mg). The reaction mixture was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1-3/2)