benzyl N-phenylcarbamate

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

Procedure: Under nitrogen, to a solution of N-benzyl-(3-methoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-yl)amine (300 mg) and 1-[N-phenyl-N-benzyloxycarbonylamino]-2,3-epoxypropane (300 mg) in dichloromethane (5 ml) was added ytterbium(III) trifluoromethanesulfonate (66 mg) at room temperature, and the mixture was stirred at the same temperature for 24 hours. The resulting mixture was poured into saturated aqueous sodium hydrogencarbonate and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by column chromatography on silica gel (hexane:ethyl acetate=10:1 to 4:1) to give N-[3-[N′-benzyl-N-(3-methoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-yl)amino]-2-hydroxypropyl[-N-benzyloxycarbonylphenylamine (307 mg). extracted with ethyl acetate The organic layer was washed with brine dried over anhydrous magnesium sulfate evaporated in vacuo The residue was purified by column chromatography on silica gel (hexane:ethyl acetate=10:1 to 4:1)

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

Procedure: In Scheme 4, aniline (62) and benzyl chloroformate (63) are reacted in the presence of NaHCO3 and acetone:water (2:1) to generate benzyl N-phenylcarbamate (64), which when reacted with Cs2CO3 and (S)-(+)-glycidyl butyrate (65), in DMF solution gives the 5-(hydroxymethyl)-3-phenyloxazolidin-2-one (66), which upon treatment with NaIO4, RuCl3, H2O generates (67).

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

Procedure: Under ice-cooling, 1.87 g of 62% sodium hydride was added to 100 ml of a dimethylformamide (DMF) solution containing 10.00 g of N-benzyloxycarbonylaniline, and the mixture was stirred at room temperature for one hour. Under ice-cooling, to the above mixture was added dropwise 50 ml of a DMF solution containing 10.31 g of ethyl 6-bromohexanoate, and the resulting mixture was stirred at room temperature overnight. DMF was removed under reduced pressure and water was added to the residue. The mixture was extracted with ethyl acetate. The extract was washed and dried, and the solvent was removed under reduced pressure. The residue was dissolved in 160 ml of methanol and 2 g of 10% palladium-carbon (Pd-C) was added to the solution. The mixture was subjected to catalytic reduction at normal temperature under normal pressure for 2 hours. After removing the catalyst by filtration, the filtrate was condensed and the residue was purified by silica gel column chromatography (solvent; hexane:ethyl acetate=4:1) to give 8.13 g of N-ethoxycarbonylpentyl-N-phenylamine (yield; 79%, melting point: 34°-37° C.). Under ice-cooling Under ice-cooling, to the above mixture the resulting mixture was stirred at room temperature overnight DMF was removed under reduced pressure and water was added to the residue The mixture was extracted with ethyl acetate The extract was washed dried the solvent was removed under reduced pressure The residue was dissolved in 160 ml of methanol 2 g of 10% palladium-carbon (Pd-C) was added to the solution The mixture was subjected to catalytic reduction at normal temperature under normal pressure for 2 hours After removing the catalyst by filtration condensed the residue was purified by silica gel column chromatography (solvent; hexane:ethyl acetate=4:1)