Hydrochloric Acid → 3-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (R)-(+)-

HRID 627201

반응식

HRID 627201 반응식
[CH3:1][C:2]1([CH3:18])[N:6]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[C@@H:5]([C:14](OC)=[O:15])[CH2:4][O:3]1.CC(C[AlH]CC(C)C)C.CO.Cl>C1(C)C=CC=CC=1>[CH:14]([C@H:5]1[CH2:4][O:3][C:2]([CH3:18])([CH3:1])[N:6]1[C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[O:15]

참가 물질

6

반응물 4

HCID 313Hydrochloric AcidHCID 887MethanolHCID 14487Diisobutylaluminum hydrideHCID 6882203-tert-butyl 4-methyl (4R)-2,2-dimethyl-1,3-oxazolidine-3,4-dicarboxylate2회

생성물 1

HCID 1787923-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (R)-(+)-수율 61.4%

시약·촉매·용매 1

HCID 1140Toluene용매

반응 조건

온도
-78 °C

실험 절차

To a −78° C. solution of (R)-3-tert-butyl 4-methyl 2,2-dimethyloxazolidine-3,4-dicarboxylate (Intermediate 181, 18.80 g, 72.50 mmol) in toluene (153 mL) was dropwise (via addition funnel) added DIBAL-H (1.0 M in toluene) (116 ml, 116.01 mmol) over 1.5 hours. The reaction mixture was stirred at −78° C. for 2 hours under nitrogen atmosphere. The cold reaction mixture was treated with 38 mL MeOH (˜1.91 M) and then poured 750 mL cold 1N HCl (˜0.09M) into reaction mixture, removed reaction mixture from −78° C. bath, transferred to separatory funnel and extracted with ethyl acetate. The organic layers were dried over magnesium sulfate, filtered, concentrated. Due to a difficult separation required two silica gel chromatography columns (0%-50% ethyl acetate/hexanes) to afford the title compound as a colorless oily solid (10.2 g, 61%).

후처리

  1. customTo a −78° C.
  2. addition(via addition funnel)
  3. customThe cold reaction mixture
  4. custominto reaction mixture
  5. customremoved
  6. customreaction mixture from −78° C. bath
  7. customtransferred to separatory funnel
  8. extractionextracted with ethyl acetate
  9. dry with materialThe organic layers were dried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customDue to a difficult separation

출처 및 근거

ORD 기록
ord-4672986452dd4412a02d6c53677cb722
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09309245B2

연결된 노트

불러오는 중…