반응 #59642

반응 방정식

acetone dichloromethane

epoxide

{(S)-2-[7-Formyl-6-((S)-1-oxiranylmethoxy)-indazol-1-yl]-1-methyl-ethyl}-carbamic acid benzyl ester

m-chloroperbenzoic acid

→

oil

수율 60.0%

[(S)-2-((R)-8-Hydroxymethyl-7,8-dihydro-[1,4]dioxino[2,3-g]indazol-1-yl)-1-methyl-ethyl]-carbamic acid benzyl ester

수율 60.0%

용매

dichloromethane

반응 조건

후처리

1. 1
   workup.ADDITIONAfter the addition
2. 2
   기타The reaction was quenched by a saturated aqueous solution of sodium thiosulfate (20 mL) and dichloromethane
3. 3
   기타was evaporated
4. 4
   workup.ADDITIONTo the aqueous residue was added potassium carbonate (1.0 g) and methanol (200 mL)
5. 5
   workup.STIRRINGthe resulting mixture was stirred for ½ h
6. 6
   기타organic solvent was evaporated
7. 7
   추출The residue was extracted with ethyl acetate (50 mL×3)
8. 8
   기타dried
9. 9
   기타evaporated to dryness
10. 10
    기타to afford an oil

실험 절차

To a stirred solution of the epoxide from Step A (0.86 g, 2.10 mmol) in dichloromethane (100 mL) was added m-chloroperbenzoic acid (70%, 0.62 g, 2.52 mmol) in portions under nitrogen atmosphere. After the addition completed the reaction mixture was stirred overnight. The reaction was quenched by a saturated aqueous solution of sodium thiosulfate (20 mL) and dichloromethane was evaporated. To the aqueous residue was added potassium carbonate (1.0 g) and methanol (200 mL), the resulting mixture was stirred for ½ h and organic solvent was evaporated. The residue was extracted with ethyl acetate (50 mL×3), dried and evaporated to dryness to afford an oil. Chromatography on silica eluting with a gradient of 0% to 10% acetone/dichloromethane gave an oil (0.50 g, 60%). LCMS (+APCI) m/z 397 (M+H), 1H NMR (600 MHz, CDCl3) δ 7.82 (s, 1H), 7.33-7.13 (m, 5H), 7.14 (d, J=8.4 Hz, 1H), 6.74 (d, J=8.4 Hz, 1H), 5.04-4.97 (m, 3H), 4.65 (ddd, J=6.6, 13.4, 51.6 Hz, 2H), 4.32 (m, 3H), 4.08 (m, 2H), 3.91 (m, 2H), 1.18(d, J=7.2 Hz, 3H).

출처