Ethyl 1-(benzyloxymethyl)-4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)cyclohex-3-enecarboxylate → Ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)-1-(hydroxymethyl)cyclohexanecarboxylate

HRID 334365노트

반응식

HRID 334365 반응식
C([O:8][CH2:9][C:10]1([C:42]([O:44][CH2:45][CH3:46])=[O:43])[CH2:15][CH2:14][C:13]([C:16]2[CH:21]=[C:20]([N:22]([CH2:31][O:32][CH2:33][CH2:34][Si:35]([CH3:38])([CH3:37])[CH3:36])[CH2:23][O:24][CH2:25][CH2:26][Si:27]([CH3:30])([CH3:29])[CH3:28])[N:19]3[N:39]=[CH:40][CH:41]=[C:18]3[N:17]=2)=[CH:12][CH2:11]1)C1C=CC=CC=1>C1COCC1.[Pd]>[CH3:29][Si:27]([CH3:28])([CH3:30])[CH2:26][CH2:25][O:24][CH2:23][N:22]([CH2:31][O:32][CH2:33][CH2:34][Si:35]([CH3:38])([CH3:37])[CH3:36])[C:20]1[N:19]2[N:39]=[CH:40][CH:41]=[C:18]2[N:17]=[C:16]([CH:13]2[CH2:12][CH2:11][C:10]([CH2:9][OH:8])([C:42]([O:44][CH2:45][CH3:46])=[O:43])[CH2:15][CH2:14]2)[CH:21]=1

참가 물질

4

반응물 1

HCID 86686664Ethyl 1-(benzyloxymethyl)-4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)cyclohex-3-enecarboxylate

생성물 1

HCID 66584374Ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)-1-(hydroxymethyl)cyclohexanecarboxylate수율 27.6%

시약·촉매·용매 2

HCID 23938Palladium촉매HCID 8028Tetrahydrofuran용매

반응 조건

온도
50 °C

실험 절차

A mixture of ethyl 1-(benzyloxymethyl)-4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)cyclohex-3-enecarboxylate (3.06 g, 4.59 mmol) and Pd/C (cat.) in THF (25 mL) was heated at 50° C. under 1.0 atm of H2 for 16 h. LCMS indicated complete reduction of double bond. The reaction mixture was filtered and evaporated. The residue was dissolved in MeOH and HCO2NH4 and Pd/C (cat.) was added. The resulting mixture was heated under reflux for 24 h. After cooling to rt, the reaction mixture was filtered. The filtrate was concentrated and purified by a SiO2 column (0-40% EtOAc/Hexanes, Rf=0.5 in 50% EtOAc) to afford ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)-1-(hydroxymethyl)cyclohexanecarboxylate as colorless oil (733 mg). HPLC-MS TR=2.78 min (UV 254 nm, 5 min method); mass calculated for formula C28H50N4O5Si2 578.3, observed LCMS m/z 579.2 (M+H).

후처리

  1. filtrationThe reaction mixture was filtered
  2. customevaporated
  3. dissolutionThe residue was dissolved in MeOH
  4. additionHCO2NH4 and Pd/C (cat.) was added
  5. temperatureThe resulting mixture was heated
  6. temperatureunder reflux for 24 h
  7. temperatureAfter cooling to rt
  8. filtrationthe reaction mixture was filtered
  9. concentrationThe filtrate was concentrated
  10. custompurified by a SiO2 column (0-40% EtOAc/Hexanes, Rf=0.5 in 50% EtOAc)

출처 및 근거

ORD 기록
ord-96d0414c7d2548a6be071e5ad75eb1e7
출처 데이터셋
uspto-grants-2014_11
특허 번호
US08883801B2

반응 노트

불러오는 중…