Diiodomethane → 2-(1,1-Dimethylethyl) 5-(9H-fluoren-9-ylmethyl) 2,5-diazabicyclo(4.1.0)heptane-2,5-dicarboxylate

HRID 2173431노트

반응식

HRID 2173431 반응식
[N:1]1([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH:6]=[CH:5][N:4]([C:7]([O:9][CH2:10][CH:11]2[C:23]3[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=3[C:17]3[C:12]2=[CH:13][CH:14]=[CH:15][CH:16]=3)=[O:8])[CH2:3][CH2:2]1.[CH2:31]([Zn]CC)C.ICI>CCOCC>[CH:6]12[CH2:31][CH:5]1[N:4]([C:7]([O:9][CH2:10][CH:11]1[C:12]3[CH:13]=[CH:14][CH:15]=[CH:16][C:17]=3[C:18]3[C:23]1=[CH:22][CH:21]=[CH:20][CH:19]=3)=[O:8])[CH2:3][CH2:2][N:1]2[C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25]

참가 물질

5

반응물 3

HCID 6346DiiodomethaneHCID 67518168HCID 67518168, 화합물HCID 178418750HCID 178418750, 화합물

생성물 1

HCID 1015019572-(1,1-Dimethylethyl) 5-(9H-fluoren-9-ylmethyl) 2,5-diazabicyclo(4.1.0)heptane-2,5-dicarboxylate

시약·촉매·용매 1

HCID 3283Diethyl Ether용매2회

실험 절차

In a pre-dried round bottom flask, tert-butyl 9H-fluoren-9-ylmethyl 2,3-dihydropyrazine-1,4-dicarboxylate (1.5 g, 3.69 mmol) was dissolved in anhydrous ether (80 ml) under N2. Diethylzinc (27.4 ml, 27.4 mmol) in ether (1M) was added in via syringe. Diiodomethane (1.904 ml, 23.60 mmol) was added. Let reaction stir at room temperature overnight. On next day, reaction was quenched by adding 5 mL of saturated aqueous NH4Cl. Reaction mixture was filtered over a pad of Celite® and filtering cake was washed with ether (25 mL×2). Then layers were separated and aqueous portion was extracted with ether (50 mL). The combined organic phases were washed with water (50 mL) and brine (50 mL), dried over anhydrous Na2SO4. Concentration at reduced pressure afforded crude product that was purified by silica gel column chromatography (40 gram silica gel column, eluted with 0-100% EtOAc/Hexane gradient). Removing solvent gave the title compound. 1H NMR (ppm) (500 MHz, CDCl3): δ 7.76 (2H, d, J=7.59 Hz), 7.66-7.53 (2H, m), 7.40 (2H, t, J=7.50 Hz), 7.31 (2H, t, J=7.45 Hz), 4.52-4.44 (2H, m), 4.26 (1H, t, J=7.13 Hz), 3.62-2.90 (6H, m), 1.50 (9H, s), 1.25-0.89 (1H, m). 0.55-0.39 (1H, m); LC/MS (M+23)+=443.13;

후처리

  1. customreaction
  2. waitOn next day
  3. customreaction
  4. customwas quenched
  5. additionby adding 5 mL of saturated aqueous NH4Cl
  6. customReaction mixture
  7. filtrationwas filtered over a pad of Celite®
  8. filtrationfiltering cake
  9. washwas washed with ether (25 mL×2)
  10. customThen layers were separated
  11. extractionaqueous portion was extracted with ether (50 mL)
  12. washThe combined organic phases were washed with water (50 mL) and brine (50 mL)
  13. dry with materialdried over anhydrous Na2SO4
  14. concentrationConcentration at reduced pressure
  15. customafforded crude product that
  16. customwas purified by silica gel column chromatography (40 gram silica gel column, eluted with 0-100% EtOAc/Hexane gradient)

출처 및 근거

ORD 기록
ord-78f9e28565124cbcbb575af77527be1a
출처 데이터셋
uspto-grants-2015_06
특허 번호
US09056859B2

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