(1-bromo-2-methyl-1-oxopropan-2-yl) acetate

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

Procedure: To a mixture of 2-amino-7-(β-D-ribofuranosyl)-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (1.8 g, 6.0 mmol) in acetonitrile (80 mL) were added a solution of H2O/CH3CN (1:9, 1.08 mL) and then a-acetoxyisobutyryl bromide (3.5 mL, 24 mmol). After 2 h stirring at room temperature, saturated aqueous NaHCO3 (170 mL) was added and the mixture was extracted with EtOAc (300+200 mL). The combined organic phase was washed with brine (100 mL), dried (Na2SO4) and evaporated to a pale yellow foamy residue. This was suspended in anhydrous MeOH (80 mL) and stirred overnight with 25 mL of DOWEX OH− resin (previously washed with anhydrous MeOH). The resin was filtered, washed thoroughly with MeOH and the combined filtrate evaporated to give a pale yellow foam (1.92 g). the mixture was extracted with EtOAc (300+200 mL) The combined organic phase was washed with brine (100 mL) dried (Na2SO4) evaporated to a pale yellow foamy residue stirred overnight with 25 mL of DOWEX OH− resin ( previously washed with anhydrous MeOH) The resin was filtered washed thoroughly with MeOH the combined filtrate evaporated

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

Procedure: To a mixture of 2-amino-7-(β-D-ribofuranosyl)-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (1.8 g, 6.0 mmol) in acetonitrile (80 mL) were added a solution of H2O/CH3CN (1:9, 1.08 mL) and then a-acetoxyisobutyryl bromide (3.5 mL, 24 mmol). After 2 h stirring at room temperature, saturated aqueous NaHCO3 (170 mL) was added and the mixture was extracted with EtOAc (300+200 mL). The combined organic phase was washed with brine (100 mL), dried (Na2SO4) and evaporated to a pale yellow foamy residue. This was suspended in anhydrous MeOH (80 mL) and stirred overnight with 25 mL of DOWEX OH− resin (previously washed with anhydrous MeOH). The resin was filtered, washed thoroughly with MeOH and the combined filtrate evaporated to give a pale yellow foam (1.92 g). the mixture was extracted with EtOAc (300+200 mL) The combined organic phase was washed with brine (100 mL) dried (Na2SO4) evaporated to a pale yellow foamy residue stirred overnight with 25 mL of DOWEX OH− resin ( previously washed with anhydrous MeOH) The resin was filtered washed thoroughly with MeOH the combined filtrate evaporated

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

Procedure: To a mixture of 2-amino-7-(β-D-ribofuranosyl)-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (1.8 g, 6.0 mmol) in acetonitrile (80 mL) were added a solution of H2O/CH3CN (1:9, 1.08 mL) and then α-acetoxyisobutyryl bromide (3.5 mL, 24 mmol). After 2 h stirring at room temperature, saturated aqueous NaHCO3 (170 mL) was added and the mixture was extracted with EtOAc (300+200 mL). The combined organic phase was washed with brine (100 mL), dried (Na2SO4) and evaporated to a pale yellow foamy residue. This was suspended in anhydrous MeOH (80 mL) and stirred overnight with 25 mL of DOWEX OH resin (previously washed with anhydrous MeOH). The resin was filtered, washed thoroughly with MeOH and the combined filtrate evaporated to give a pale yellow foam (1.92 g). the mixture was extracted with EtOAc (300+200 mL) The combined organic phase was washed with brine (100 mL) dried (Na2SO4) evaporated to a pale yellow foamy residue stirred overnight with 25 mL of DOWEX OH resin ( previously washed with anhydrous MeOH) The resin was filtered washed thoroughly with MeOH the combined filtrate evaporated

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

Procedure: To a stirred solution of diol 23 (7.42 g, 22.1 mmol) in THF (150 mL) at 0° C. under nitrogen atmosphere, α-acetoxyisobutyryl bromide (4.1 mL, 27.8 mmol) was added dropwise over a period of 10 min. The reaction mixture was stirred at same temperature for 30 min, and warmed to room temperature with stirring for 3.5 h. The solvent was evaporated, and the residual oil was partitioned between EtOAc (200 mL) and 5% aqueous NaHCO3 (50 mL). The organic layer was washed with water (100 mL), dried over MgSO4, filtered and concentrated to afford the crude bromoacetate 24 (9.05 g). The crude product was used in the next step without further purification. with stirring for 3.5 h The solvent was evaporated the residual oil was partitioned between EtOAc (200 mL) and 5% aqueous NaHCO3 (50 mL) The organic layer was washed with water (100 mL) dried over MgSO4 filtered concentrated

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

Procedure: To a mixture of 2-amino-7-(β-D-ribofuranosyl)-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (1.8 g, 6.0 mmol) in acetonitrile (80 mL) were added a solution of H2O/CH3CN (1:9, 1.08 mL) and then α-acetoxyisobutyryl bromide (3.5 mL, 24 mmol). After 2 h stirring at room temperature, saturated aqueous NaHCO3 (170 mL) was added and the mixture was extracted with EtOAc (300+200 mL). The combined organic phase was washed with brine (100 mL), dried (Na2SO4) and evaporated to a pale yellow foamy residue. This was suspended in anhydrous MeOH (80 mL) and stirred overnight with 25 mL of DOWEX OH− resin (previously washed with anhydrous MeOH). The resin was filtered, washed thoroughly with MeOH and the combined filtrate evaporated to give a pale yellow foam (1.92 g). the mixture was extracted with EtOAc (300+200 mL) The combined organic phase was washed with brine (100 mL) dried (Na2SO4) evaporated to a pale yellow foamy residue stirred overnight with 25 mL of DOWEX OH− resin ( previously washed with anhydrous MeOH) The resin was filtered washed thoroughly with MeOH the combined filtrate evaporated

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

Procedure: To a mixture of 2-amino-7-(β-D-ribofuranosyl)-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (1.8 g, 6.0 mmol) in acetonitrile (80 mL) were added a solution of H2O/CH3CN (1:9, 1.08 mL) and then α-acetoxyisobutyryl bromide (3.5 mL, 24 mmol). After 2 h stirring at room temperature, saturated aqueous NaHCO3 (170 mL) was added and the mixture was extracted with EtOAc (300+200 mL). The combined organic phase was washed with brine (100 mL), dried (Na2SO4) and evaporated to a pale yellow foamy residue. This was suspended in anhydrous MeOH (80 mL) and stirred overnight with 25 mL of DOWEX OH− resin (previously washed with anhydrous MeOH). The resin was filtered, washed thoroughly with MeOH and the combined filtrate evaporated to give a pale yellow foam (1.92 g). the mixture was extracted with EtOAc (300+200 mL) The combined organic phase was washed with brine (100 mL) dried (Na2SO4) evaporated to a pale yellow foamy residue stirred overnight with 25 mL of DOWEX OH− resin ( previously washed with anhydrous MeOH) The resin was filtered washed thoroughly with MeOH the combined filtrate evaporated