tert-butyl N-[2-(hydroxymethyl)phenyl]carbamate

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

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

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

Procedure: A 20% dispersion of pyridinium chlorochromate in basic alumina (50 g) was added to a solution of tert-butyl N-[2-(hydroxymethyl)phenyl]carbamate (11.0 g, 0.0493 mol) in anhydrous chloroform and the resulting suspension was stirred under an atmosphere of nitrogen at ambient temperature for 1 hour. Additional 16 g of a 20% dispersion of pyridinium chlorochromate in basic alumina was added and the stirring was continued for 45 min. At this point in time, additional 15 g of of 20% dispersion of pyridinium chlorochromate in basic alumina was added and the stirring was continued for 25 min. The resulting suspension was filtered through a silica gel pad, the filtrate was concentrated under reduced pressure and the residue purified by flash chromatography on silica using ethyl acetate/n-heptane (2:98) as mobile phase to yield tert-butyl N-(2-formylphenyl)carbamate (8.67 g, 0.0392 mol) as a white solid. the stirring was continued for 45 min the stirring was continued for 25 min The resulting suspension was filtered through a silica gel pad the filtrate was concentrated under reduced pressure the residue purified by flash chromatography on silica

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

Procedure: To a solution of imidazole (404 mg, 5.94 mmol) and triphenylphosphine (1.56 g, 5.94 mmol) in methylene chloride (50 mL) is added iodine (1.51 g, 5.94 mmol) in portions. When the reaction is complete, a solution of (2-hydroxymethylphenyl)-carbamic acid tert-butyl ester (1.2 g, 5.4 mmol) in methylene chloride (20 mL) is added dropwise and the mixture is stirred at RT for 75 min. The mixture is concentrated and the insoluble material is filtered. The filtrate is evaporated and the residue is purified by column chromatography using a gradient of 25-50% MTBE/methylene chloride as eluent to give the title compound. The mixture is concentrated the insoluble material is filtered The filtrate is evaporated the residue is purified by column chromatography

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

Procedure: To a solution of imidazole (404 mg, 5.94 mmol) and triphenylphosphine (1.56 g, 5.94 mmol) in methylene chloride (50 mL) is added iodine (1.51 g, 5.94 mmol) in portions. When the reaction is complete, a solution of (2-hydroxymethylphenyl)-carbamic acid tert-butyl ester (1.2 g, 5.4 mmol) in methylene chloride (20 mL) is added dropwise and the mixture is stirred at RT for 75 min. The mixture is concentrated and the insoluble material is filtered. The filtrate is evaporated and the residue is purified by column chromatography using a gradient of 25-50% MTBE/methylene chloride as eluent to give the title compound. The mixture is concentrated the insoluble material is filtered The filtrate is evaporated the residue is purified by column chromatography

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

Procedure: A 20% dispersion of pyridinium chlorochromate in basic alumina (50 g) was added to a solution of tert-butyl N-[2-(hydroxymethyl)phenyl]carbamate (11.0 g, 0.0493 mol) in anhydrous chloroform and the resulting suspension was stirred under an atmosphere of nitrogen at ambient temperature for 1 hour. Additional 16 g of a 20% dispersion of pyridinium chlorochromate in basic alumina was added and the stirring was continued for 45 min. At this point in time, additional 15 g of of 20% dispersion of pyridinium chlorochromate in basic alumina was added and the stirring was continued for 25 min. The resulting suspension was filtered through a silica gel pad, the filtrate was concentrated under reduced pressure and the residue purified by flash chromatography on silica using ethyl acetate/n-heptane (2:98) as mobile phase to yield tert-butyl N-(2-formylphenyl)carbamate (8.67 g, 0.0392 mol) as a white solid. the stirring was continued for 45 min the stirring was continued for 25 min The resulting suspension was filtered through a silica gel pad the filtrate was concentrated under reduced pressure the residue purified by flash chromatography on silica

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

Procedure: A 20% dispersion of pyridinium chlorochromate in basic alumina (50 g) was added to a solution of tert-butyl N-[2-(hydroxymethyl)phenyl]carbamate (11.0 g, 0.0493 mol) in anhydrous chloroform and the resulting suspension was stirred under an atmosphere of nitrogen at ambient temperature for 1 hour. Additional 16 g of a 20% dispersion of pyridinium chlorochromate in basic alumina was added and the stirring was continued for 45 min. At this point in time, additional 15 g of of 20% dispersion of pyridinium chlorochromate in basic alumina was added and the stirring was continued for 25 min. The resulting suspension was filtered through a silica gel pad, the filtrate was concentrated under reduced pressure and the residue purified by flash chromatography on silica using ethyl acetate/n-heptane (2:98) as mobile phase to yield tert-butyl N-(2-formylphenyl)carbamate (8.67 g, 0.0392 mol) as a white solid. the stirring was continued for 45 min the stirring was continued for 25 min The resulting suspension was filtered through a silica gel pad the filtrate was concentrated under reduced pressure the residue purified by flash chromatography on silica

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

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

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1.3 g of tert-butyl (2-hydroxymethylphenyl)carbamate were dissolved in 20 ml of dichloromethane; at 5° C., a solution of 630 mg of phosphorus tribromide in 5 ml of DCM was then added dropwise. The reaction mixture was subsequently stirred at 5° C. for 2 h. For workup, the mixture was admixed cautiously with solid sodium hydrogencarbonate and 1 ml of water, stirred at 5° C. for 30 min, filtered through a cartridge and concentrated under reduced pressure. tert-Butyl (2-bromomethylphenyl)carbamate was obtained in a 67% yield. 1H NMR: 8.71, s, 1H, 7.45, d, 1H, 7.42, d, 1H, 7.3, t, 1H, 7.1, t, 1H; 4.78, 2, 2H, 1.45, s, 9H. stirred at 5° C. for 30 min filtered through a cartridge concentrated under reduced pressure

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

Procedure: To a solution of (2-hydroxymethyl-phenyl)-carbamic acid tert-butyl ester (0.8 g; 3.6 mmol) in EtOAc (15 ml) at 0° C. is added NEt3 (610 μl) and methanesulfonyl chloride (340 μl). After addition the mixture is warmed to RT and stirred for 3 days. After completion the reaction mixture is acidified with diluted hydrochloric acid and extracted twice with EtOAc. The organic phase is washed with brine, dried over MgSO4 and evaporated to give methanesulfonic acid 2-tert-butoxycarbonylamino-benzyl ester (0.73 g). After addition the mixture extracted twice with EtOAc The organic phase is washed with brine dried over MgSO4 evaporated

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (2-Hydroxymethyl-phenyl)-carbamic acid tert-butyl ester (44.7 g, 0.200 mol), CH2Cl2 (625 mL) and manganese(IV) oxide (85%, 5 μm powder; 245.5 g, 2.400 mol) were introduced into a flask. The mixture was stirred at 40° C. for at least 4 h or until HPLC analysis showed that the reaction had proceeded to greater than 97% completion. The cooled mixture was filtered through a Celite pad (22 g) and the filter cake was rinsed with CH2Cl2 (625 mL). The filtrate and wash were concentrated in vacuo to dryness to afford the title compound as an oily yellow material (44 g, 99% yield). The cooled mixture was filtered through a Celite pad (22 g) the filter cake was rinsed with CH2Cl2 (625 mL) The filtrate and wash were concentrated in vacuo to dryness