反応 #74435

反応方程式

potassium carbonate

hydrazine

2-((1R,2S,4R,5S)-5-(tert- butyldiphenylsilyloxy)bicyclo[2.2.1]-heptan-2-yl)isoindoline-1,3-dione

benzoyl isothiocyanate

→

title compound

1-((1R,2S,4R,5S)-5-(tert-Butyldiphenylsilyloxy)bicyclo[2.2.1]heptan-2-yl)thiourea

溶媒

methanol

dichloromethane

ethanol

chloroform

反応条件

後処理

1. 1
   温度After refluxing under nitrogen for 3 h
2. 2
   その他The white solid was removed by filtration
3. 3
   濃縮the filtrate was concentrated in vacuo
4. 4
   その他to give an off-white solid, which
5. 5
   その他the solid was removed by filtration
6. 6
   濃縮The filtrate was concentrated
7. 7
   その他to give an off-white solid, which
8. 8
   その他The solvents were removed in vacuo
9. 9
   その他the residue was partitioned between EtOAc and water
10. 10
    その他The organic portion was separated
11. 11
    洗浄washed with brine
12. 12
    その他The residue was purified by flash column chromatography (0 to 60% of EtOAc in hexanes)

実験手順

To a suspension of 2-((1R,2S,4R,5S)-5-(tert- butyldiphenylsilyloxy)bicyclo[2.2.1]-heptan-2-yl)isoindoline-1,3-dione (4.60 g, 9.28 mmol) in ethanol (anhydrous, 100 mL) was added anhydrous hydrazine (0.44 mL, 13.9 mmol). After refluxing under nitrogen for 3 h, the mixture was cooled to ambient temp. The white solid was removed by filtration, and the filtrate was concentrated in vacuo to give an off-white solid, which was stirred with benzoyl isothiocyanate (1.62 mL, 12.1 mmol) in chloroform (100 mL) at ambient temp. overnight. The reaction mixture was diluted with dichloromethane (50 mL) and the solid was removed by filtration. The filtrate was concentrated to give an off-white solid, which was stirred with potassium carbonate (3.85 g, 27.8 mmol) in methanol (100 mL) at ambient temp. for 30 min. The solvents were removed in vacuo, and the residue was partitioned between EtOAc and water. The organic portion was separated, washed with brine, and conc. in vacuo. The residue was purified by flash column chromatography (0 to 60% of EtOAc in hexanes) to give the title compound as a white solid. MS m/z: 425.2 (M+H)+.

出典