Methyl iodide → (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)pent-4-en-2-yl(methyl)carbamate

HRID 409759노트

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HRID 409759 반응식
[Si:1]([O:8][CH2:9][C@@H:10]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[CH2:11][CH:12]=[CH2:13])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH3:22]I.[H-].[Na+]>CN(C=O)C>[Si:1]([O:8][CH2:9][C@@H:10]([N:14]([CH3:22])[C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[CH2:11][CH:12]=[CH2:13])([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:3])[CH3:2]

참가 물질

5

반응물 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 14153345(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)pent-4-en-2-ylcarbamate

생성물 1

HCID 57947449(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)pent-4-en-2-yl(methyl)carbamate수율 121.4%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

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온도
0 °C

실험 절차

To a solution of (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)pent-4-en-2-ylcarbamate (95 g, 0.3 mol) and MeI (46.7 mL, 0.75 mol) in DMF (500 mL) was added sodium hydride (60%, 18 g, 0.45 mol) at 0° C. The reaction was stirred at 0° C. for 3 h and LC-MS showed the reaction was complete. The reaction was quenched with saturated NH4Cl solution and filtered. The filtrate was concentrated to remove most of DMF and the residue was dissolved in EtOAc (1.5 L). The organic layer was washed with water and brine, dried over Na2SO4. The above steps were repeated with another 127 g of (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)pent-4-en-2-ylcarbamate. The organic layers were combined and concentrated. The resulting residue was purified on silica gel column using a mixture of hexanes and EtOAc to give (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)pent-4-en-2-yl(methyl)carbamate (120 g, 40% for 4 steps). LRMS (M+H+) m/z 230.2.

후처리

  1. customThe reaction was quenched with saturated NH4Cl solution
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated
  4. customto remove most of DMF
  5. dissolutionthe residue was dissolved in EtOAc (1.5 L)
  6. washThe organic layer was washed with water and brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customThe resulting residue was purified on silica gel column
  10. additiona mixture of hexanes and EtOAc

출처 및 근거

ORD 기록
ord-aa0a09b38a7642669c7c25398f67d5ed
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08759374B2

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