反应详情

In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), to an ice-cold solution of trans-4-benzyloxycarbonylaminocyclohexane-methanol (1.32 g, 5.01 mmol), triphenylphoshine on polystyrene (15.04 mmol) and imidazole (483 mg, 7.02 mmol) in dry CH2Cl2 (150 mL) was added iodine (2.06 g, 8.02 mmol). The reaction mixture was warmed to rt and stirred at this temperature until completion of the reaction. The mixture was then filtered, successively washed with 10% aq. Na2SO3 and brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The crude iodide (1.64 g, 4.39 mmol) was redissolved in DMF (15 mL) and treated with sodium azide (303 mg, 4.61 mmol). The reaction mixture was heated to 80° C. until completion of the reaction. The mixture was then diluted with EA, washed with brine (3×), dried over MgSO4, filtered and concentrated under reduced pressure. To a mixture of the crude azide (1.27 g, 4.40 mmol) in THF (21 mL) were added polymer-supported Ph3P (2.0 eq.) and water (7 mL). The reaction mixture was stirred at 55° C. until completion of the reaction, cooled down to rt and filtered. The filtrate was partitioned between EA and aq. 0.5M Na2CO3 and the layers separated. The aq. layer was extracted with EA (2×) and the combined org. extracts dried over MgSO4, filtered and concentrated under reduced pressure to give benzyl (trans-4-(aminomethyl)cyclohexyl)carbamate as a white solid. LC-MS-conditions 07b: tR=0.57 min; [M+H]+=263.46.

1. filtrationThe mixture was then filtered
2. washsuccessively washed with 10% aq. Na2SO3 and brine
3. dry with materialdried over Na2SO4
4. filtrationfiltered
5. concentrationconcentrated under reduced pressure
6. temperatureThe reaction mixture was heated to 80° C. until completion of the reaction
7. washwashed with brine (3×)
8. dry with materialdried over MgSO4
9. filtrationfiltered
10. concentrationconcentrated under reduced pressure
11. stirringThe reaction mixture was stirred at 55° C. until completion of the reaction
12. temperaturecooled down to rt
13. filtrationfiltered
14. customThe filtrate was partitioned between EA and aq. 0.5M Na2CO3
15. customthe layers separated
16. extractionThe aq. layer was extracted with EA (2×)
17. dry with materialextracts dried over MgSO4
18. filtrationfiltered
19. concentrationconcentrated under reduced pressure