反応 #88967

反応方程式

iodomethane

diacetone α-D-glucose

THF

NaH

THF

carbon disulfide

→

O-[(3aR,5R,6S,6aR)-5-(2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl] methylsulfanylmethanethioate

反応条件

後処理

1. 1
   その他temperature below 15° C
2. 2
   workup.STIRRINGthe reaction mixture was stirred at room temperature for 1 hour
3. 3
   workup.STIRRINGstirred at room temperature for another 2 hours
4. 4
   その他quenched by saturated NH4Cl solution (70 mL)
5. 5
   抽出extracted with EtOAc (100 mL) twice
6. 6
   乾燥The combined organic layers were dried over Na2SO4
7. 7
   濃縮concentrated in vacuo
8. 8
   その他The residue was purified by column chromatography on silica gel (eluting with 1:10 EtOAc in petroleum ether)

実験手順

To a suspension of NaH (60% in mineral oil, 4 g, 100 mmol) in THF (80 mL) was added a solution of diacetone-α-D-glucose (10.5 g, 40 mmol) and imidazole (136 mg, 2 mmol) in THF (20 mL) dropwise while keeping inner temperature below 15° C. The formed mixture was stirred at 10° C. for 15 minutes. To the previous mixture was added carbon disulfide (14.8 g, 200 mmol) and the reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was added iodomethane (24.6 g, 200 mmol) and stirred at room temperature for another 2 hours, then quenched by saturated NH4Cl solution (70 mL) and extracted with EtOAc (100 mL) twice. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 1:10 EtOAc in petroleum ether) to afford 14.6 g of O-[(3aR,5R,6S,6aR)-5-(2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl] methylsulfanylmethanethioate (compound 1a) as a colorless oil.

出典