반응 #2146712

반응 방정식

19

5-tert-Butoxycarbonylamino-5-{2-[4-(5-hydroxyl-1-pentyl)phenyl]ethyl}-2,2-dimethyl-1,3-dioxane

N,N-diisopropylethylamine

lithium iodide

sodium azide

Methanesulfonyl chloride

→

20

수율 67.0%

5-tert-Butoxycarbonylamino-5-{2-[4-(5-azido-1-pentyl)phenyl]ethyl}-2,2-dimethyl-1,3-dioxane

수율 67.0%

용매

Water

CH2Cl2

반응 조건

후처리

1. 1
   기타at room temperature
2. 2
   기타overnight
3. 3
   세척The mixture was washed with saturated aqueous NaHCO3 solution (2×10 mL), water (2×10 mL), and brine (2×10 mL)
4. 4
   건조dried (Na2SO4)
5. 5
   기타After the solvent was removed
6. 6
   workup.DISSOLUTIONthe residue was dissolved in dry DMF (5 mL)
7. 7
   workup.STIRRINGThe reaction mixture was stirred at 80° C. for 18 h
8. 8
   온도was cooled to room temperature
9. 9
   추출the suspension was extracted with CH2Cl2 (3×20 mL)
10. 10
    세척The combined organic layer was washed with water (3×30 mL) and brine (2×20 mL)
11. 11
    건조dried (Na2SO4)
12. 12
    농축concentrated under vacuum
13. 13
    기타The residue was purified by chromatography (hexanes/EtOAc 4:1)

실험 절차

A solution of 19 (168 mg, 0.40 mmol) and N,N-diisopropylethylamine (155 mg, 1.2 mmol) in CH2Cl2 (10 mL) was cooled to 0° C. Methanesulfonyl chloride (66 mg, 0.60 mmol) was added, and the mixture was stirred at 0° C. for 2 h and then at room temperature overnight. The mixture was washed with saturated aqueous NaHCO3 solution (2×10 mL), water (2×10 mL), and brine (2×10 mL), and then dried (Na2SO4). After the solvent was removed, the residue was dissolved in dry DMF (5 mL) and lithium iodide (7 mg, 48 μmol) and sodium azide (78 mg, 1.2 mmol) were added. The reaction mixture was stirred at 80° C. for 18 h and then was cooled to room temperature. Water (15 mL) was added, and the suspension was extracted with CH2Cl2 (3×20 mL). The combined organic layer was washed with water (3×30 mL) and brine (2×20 mL), dried (Na2SO4), and concentrated under vacuum. The residue was purified by chromatography (hexanes/EtOAc 4:1) to give 20 (119 mg, 67%). 1H NMR δ 7.14-7.04 (m, 4H), 5.02 (s, 1H), 3.89 (d, 2H, J=11.6 Hz), 3.67 (d, 2H, J=11.6 Hz), 3.24 (t, 2H, J=7.2 Hz), 2.60-2.50 (m, 4H), 1.97 (t, 2H, J=8.0 Hz), 1.66-1.56 (m, 4H), 1.47 (s, 9H), 1.43 (s, 3H), 1.41 (s, 3H), 1.40-1.36 (m, 2H); 13C NMR δ 154.7, 139.7, 139.2, 128.3, 128.2, 98.2, 79.1, 66.2, 51.6, 51.2, 35.2, 33.5, 30.9, 28.6, 28.5, 28.3, 27.3, 26.2, 19.6. HRMS m/z: calcd for C24H38N4NaO4 (MNa+), 469.2785; found, 469.2786.

출처