Reacción #80471

Ecuación de reacción

n-BuLi

(2S-trans)-3-methyloxiranemethanol 4-methylbenzenesulfonate

N,O-diphenoxycarbonylhydroxylamine

triphenylphosphine

DEAD

→

(R)-N,O-bis(phenoxycarbonyl)-N-(3-butyn-2-yl)hydroxylamine

Disolventes

THF

acetic acid

Condiciones de reacción

Tratamiento posterior

1. 1
   Otroafter consumption of all the rosylate (monitored by TLC)
2. 2
   workup.ADDITIONsodium bicarbonate (600 mg) was added
3. 3
   workup.ADDITIONwere added to the filtrate
4. 4
   Otrodid not rise above ambient temperature
5. 5
   Concentraciónconcentrated in vacuo

Procedimiento

A solution of (2S-trans)-3-methyloxiranemethanol 4-methylbenzenesulfonate (484 mg; 2 mmol), prepared as in step 1, in dry THF (20 ml) was treated at -70° C. to -60° C. with n-BuLi (1.6M in hexane, 7.5 ml, 12 mmol) under an atmosphere of nitrogen. Glacial acetic acid (1 ml) was added after consumption of all the rosylate (monitored by TLC). After 15 min, sodium bicarbonate (600 mg) was added and the reaction mixture was allowed to warm to room temperature. After filtration through Celite, N,O-diphenoxycarbonylhydroxylamine (550 mg, 2.00 mmol) and triphenylphosphine (786 mg, 3.00 mmol) were added to the filtrate. The resulting mixture was treated with DEAD (0.5 ml, 3.0 mmol), taking care that the reaction temperature did not rise above ambient temperature. The reaction mixture was stirred at room temperature for 16 hours and then concentrated in vacuo. The residue was purifed by chromatography on silica-gel (10% ethyl acetate/hexane) to give (R)-N,O-bis(phenoxycarbonyl)-N-(3-butyn-2-yl)hydroxylamine(contaminated with phenol).

Fuente