Triphenylphosphine → (R)-2-[2-bromo-4-fluoro-6-(prop-1-enyl)phenoxy]but-3-enyl 4-methylbenzenesulfonate

HRID 902315노트

반응식

HRID 902315 반응식
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[C:4]([CH:9]=[CH:10][CH3:11])[C:3]=1[OH:12].O[C@@H:14]([CH:27]=[CH2:28])[CH2:15][O:16][S:17]([C:20]1[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=1)(=[O:19])=[O:18].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH3:26][C:23]1[CH:24]=[CH:25][C:20]([S:17]([O:16][CH2:15][C@H:14]([O:12][C:3]2[C:4]([CH:9]=[CH:10][CH3:11])=[CH:5][C:6]([F:8])=[CH:7][C:2]=2[Br:1])[CH:27]=[CH2:28])(=[O:19])=[O:18])=[CH:21][CH:22]=1

참가 물질

6

반응물 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 7015761(S)-3-Butene-1,2-diol-1-(p-toluenesulfonate)HCID 691167852-Bromo-4-fluoro-6-(prop-1-enyl)phenol

생성물 1

HCID 86609112(R)-2-[2-bromo-4-fluoro-6-(prop-1-enyl)phenoxy]but-3-enyl 4-methylbenzenesulfonate수율 82%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of 2-bromo-4-fluoro-6-(prop-1-enyl)phenol, prepared in Example 37, step 4 (4.5 g, 0.019 mol) and (S)-toluene-4-sulfonic acid 2-hydroxy-but-3-enyl ester (7.07 g, 0.028 mol) and triphenylphosphine (11.22 g, 0.043 mol) in anhydrous THF (200 mL) at room temperature was added diethyl azodicarboxylate (7.7 mL, 0.047 mol) then the reaction mixture stirred at room temperature for 19 hours. The reaction was quenched by the addition of water (100 mL), stirred vigorously for 5 minutes and the resulting oily suspension extracted with methylene chloride (300 mL). The organic phase was separated, washed with water (2×100 mL), and saturated brine (100 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to afford a yellow oil. Purification by flash chromatography using a solvent gradient of 0 to 20% ethyl acetate in hexane gave 7.26 g (82%) of (R)-2-[2-bromo-4-fluoro-6-(prop-1-enyl)phenoxy]but-3-enyl 4-methylbenzenesulfonate as a colorless oil. MS (ES) m/z 472.1 ([M+NH4]+).

후처리

  1. customThe reaction was quenched by the addition of water (100 mL)
  2. stirringstirred vigorously for 5 minutes
  3. extractionthe resulting oily suspension extracted with methylene chloride (300 mL)
  4. customThe organic phase was separated
  5. washwashed with water (2×100 mL), and saturated brine (100 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto afford a yellow oil
  10. customPurification by flash chromatography

출처 및 근거

ORD 기록
ord-eb566c39d7604a188aefb9c85ac2dc86
출처 데이터셋
uspto-grants-2008_04
특허 번호
US07365095B2

반응 노트

불러오는 중…