trimethylsilylmethyl trifluoromethanesulfonate

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Under nitrogen atmosphere (trimethylsilyl)methyl trifluoromethanesulfonate (16.3 mmol) is added dropwise to a mixture of 2-methylthio-1,3-thiazole (15.5 mmol) in MeCN (75 mL). The mixture is treated with propynoic acid ethyl ester (23.2 mmol), kept with occasional shaking for 30 min at RT and added dropwise to a vigorously stirred solution of CsF (21.7 mmol) and propynoic acid ethyl ester (23.2 mmol) in MeCN (75 mL). After stirring for 1 h the mixture is concentrated in vacuo, diluted with DCM (100 mL), washed twice with water and twice with brine and dried over Na2SO4. The solvents are removed in vacuo and the residue is purified by FC (gradient: heptane to heptane/EtOAc 8/2) to give the desired product. After stirring for 1 h the mixture is concentrated in vacuo diluted with DCM (100 mL) washed twice with water and twice with brine dried over Na2SO4 The solvents are removed in vacuo the residue is purified by FC (gradient: heptane to heptane/EtOAc 8/2)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a pre-cooled solution of 1,2,3,5-tetra-O-benzoyl-2-C-methyl-D-ribofuranose [Harry-O'kuru, Rogers E.; Smith, Jennifer M.; Wolfe, Michael S, “A Short, Flexible Route toward 2′-C-Branched Ribonucleosides,” J. Org. Chem., 62:1754-1759 (1997)] (1.74 g, 3.00 mmol) in acetonitrile (15 mL) was added 2-amino-6-chloropurine (0.56 g, 3.30 mmol), then diazabicyclo[5.4.0]undec-7-ene (DBU) (1.37 g, 9.00 mmol), and then dropwise trimethylsilylmethyl trifluoromethanesulfonate (TMS trifate) (2.67 g, 12.00 mmol). The resulting mixture was heated to 65° C. for 4 h, then cooled and partitioned between saturated aqueous sodium bicarbonate (200 mL) and dichloromethane (200 mL). The organic phase was dried over magnesium sulfate, filtered and evaporated in vacuo. The resulting crude product was used directly in step B. cooled partitioned between saturated aqueous sodium bicarbonate (200 mL) and dichloromethane (200 mL) The organic phase was dried over magnesium sulfate filtered evaporated in vacuo

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a pre-cooled solution of 1,2,3,5-tetra-O-benzoyl-2-C-methyl-D-ribofuranose [Harry-O'kuru, Rogers E.; Smith, Jennifer M.; Wolfe, Michael S, “A Short, Flexible Route toward 2′-C-Branched Ribonucleosides,” J. Org. Chem., 62:1754-1759 (1997)] (1.74 g, 3.00 mmol) in acetonitrile (15 mL) was added 2-amino-6-chloropurine (0.56 g, 3.30 mmol), then diazabicyclo[5.4.0]undec-7-ene (DBU) (1.37 g, 9.00 mmol), and then dropwise trimethylsilylmethyl trifluoromethanesulfonate (TMS trifate) (2.67 g, 12.00 mmol). The resulting mixture was heated to 65° C. for 4 h, then cooled and partitioned between saturated aqueous sodium bicarbonate (200 mL) and dichloromethane (200 mL). The organic phase was dried over magnesium sulfate, filtered and evaporated in vacuo. The resulting crude product was used directly in step B. cooled partitioned between saturated aqueous sodium bicarbonate (200 mL) and dichloromethane (200 mL) The organic phase was dried over magnesium sulfate filtered evaporated in vacuo

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a pre-cooled solution of 1,2,3,5-tetra-O-benzoyl-2-C-methyl-D-ribofuranose [Harry-O'kuru, Rogers E.; Smith, Jennifer M.; Wolfe, Michael S, “A Short, Flexible Route toward 2′-C-Branched Ribonucleosides,” J. Org. Chem., 62:1754-1759 (1997)] (1.74 g, 3.00 mmol) in acetonitrile (15 mL) was added 2-amino-6-chloropurine (0.56 g, 3.30 mmol), then diazabicyclo[5.4.0]undec-7-ene (DBU) (1.37 g, 9.00 mmol), and then dropwise trimethylsilylmethyl trifluoromethanesulfonate (TMS trifate) (2.67 g, 12.00 mmol). The resulting mixture was heated to 65° C. for 4 h, then cooled and partitioned between saturated aqueous sodium bicarbonate (200 mL) and dichloromethane (200 mL). The organic phase was dried over magnesium sulfate, filtered and evaporated in vacuo. The resulting crude product was used directly in step B. cooled partitioned between saturated aqueous sodium bicarbonate (200 mL) and dichloromethane (200 mL) The organic phase was dried over magnesium sulfate filtered evaporated in vacuo

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

Procedure: Under nitrogen atmosphere (trimethylsilyl)methyl trifluoromethanesulfonate (16.3 mmol) is added dropwise to a mixture of 2-methylthio-1,3-thiazole (15.5 mmol) in acetonitrile (75 mL). The mixture is treated with propynoic acid ethyl ester (23.2 mmol), kept with occasional shaking for 30 min at RT and added dropwise to a vigorously stirred solution of CsF (21.7 mmol) and propynoic acid ethyl ester (23.2 mmol) in acetonitrile (75 mL). After stirring for 1 h the mixture is concentrated in vacuo, diluted with DCM (100 mL), washed twice with water and twice with brine and dried over Na2SO4. The solvents are removed in vacuo and the residue is purified by flash chromatography (gradient: heptane to heptane/EtOAc 8/2) to give the desired product. LC-MS: tR=0.87 min; [M+H]+=196.0. After stirring for 1 h the mixture is concentrated in vacuo diluted with DCM (100 mL) washed twice with water and twice with brine dried over Na2SO4 The solvents are removed in vacuo the residue is purified by flash chromatography (gradient: heptane to heptane/EtOAc 8/2)

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

Procedure: Potassium carbonate (6 g) was added to a solution of 3.5 g (0.0148 mol) of trimethylsilylmethyl trifluoromethanesulfonate and 2.3 g of 2-fluoro-2,2-dinitroethanol in 5 ml of methylene chloride, and the mixture was stirred for 16 hrs. This suspension was added with stirring to a mixture of 30 ml of ice water and 30 ml of carbon tetrachloride. The carbon tetrachloride layer was washed with 10 ml of water, dried over magnesium sulfate, and distilled to give 1.56 g (45%) of trimethylsilylmethyl 2-fluoro-2,2-dinitroethyl ether, bp 52° (0.75 mm). This suspension was added The carbon tetrachloride layer was washed with 10 ml of water dried over magnesium sulfate distilled

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

Procedure: Under nitrogen atmosphere (trimethylsilyl)methyl trifluoromethanesulfonate (16.3 mmol) is added dropwise to a mixture of 2-methylthio-1,3-thiazole (15.5 mmol) in MeCN (75 mL). The mixture is treated with propynoic acid ethyl ester (23.2 mmol), kept with occasional shaking for 30 min at RT and added dropwise to a vigorously stirred solution of CsF (21.7 mmol) and propynoic acid ethyl ester (23.2 mmol) in MeCN (75 mL). After stirring for 1 h the mixture is concentrated in vacuo, diluted with DCM (100 mL), washed twice with water and twice with brine and dried over Na2SO4. The solvents are removed in vacuo and the residue is purified by FC (gradient: heptane to heptane/EtOAc 8/2) to give the desired product. After stirring for 1 h the mixture is concentrated in vacuo diluted with DCM (100 mL) washed twice with water and twice with brine dried over Na2SO4 The solvents are removed in vacuo the residue is purified by FC (gradient: heptane to heptane/EtOAc 8/2)