Dichloromethane → (S)-2-(Benzhydrylidene-amino)-3-(3-bromo-4-fluoro-phenyl)-propionic acid tert-butyl ester

HRID 2265307노트

반응식

HRID 2265307 반응식
[C:1]([O:5][C:6](=[O:22])[CH2:7][N:8]=[C:9]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)([CH3:4])([CH3:3])[CH3:2].C=CCOC(C1C2C(=CC=CC=2)N=CC=1)C1[N+]2(CC3C4C(=CC=CC=4)C=C4C=3C=CC=C4)CC(C=C)C(CC2)C1.[Br-].C(Cl)Cl.[Br:67][C:68]1[CH:69]=[C:70]([CH:73]=[CH:74][C:75]=1[F:76])[CH2:71]Br>CCOCC.O>[C:1]([O:5][C:6](=[O:22])[C@@H:7]([N:8]=[C:9]([C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)[CH2:71][C:70]1[CH:73]=[CH:74][C:75]([F:76])=[C:68]([Br:67])[CH:69]=1)([CH3:4])([CH3:2])[CH3:3]

참가 물질

7

반응물 4

HCID 6344DichloromethaneHCID 688171N-(Diphenylmethylene)glycine tert-butyl esterHCID 129227103-Bromo-4-fluorobenzyl BromideHCID 223245784-[[1-(Anthracen-9-ylmethyl)-5-ethenyl-1-azoniabicyclo[2.2.2]octan-2-yl]-prop-2-enoxymethyl]quinoline;bromide

생성물 1

HCID 86761241(S)-2-(Benzhydrylidene-amino)-3-(3-bromo-4-fluoro-phenyl)-propionic acid tert-butyl ester수율 74%

시약·촉매·용매 2

HCID 962Water용매HCID 3283Diethyl Ether용매

반응 조건

온도
-55 °C

실험 절차

To a flame-dried flask was added (benzhydrylidene-amino)-acetic acid tert-butyl ester (250 mg, 0.846 mmol), O-allyl-N-(9-anthracenylmethyl)-cinchonidinium bromide (51 mg, 0.085 mmol), and DCM (5 mL). The flask was cooled to −55° C. and CsOH.H2O (1.4 g, 8.46 mmol) was added. The mixture was stirred for 30 min, treated with 3-bromo-4-fluorobenzyl bromide (1.1 g, 4.23 mmol), and stirred at −55° C. overnight. The mixture was diluted with Et2O (5 mL) and water (10 mL), warmed to rt, and washed with water and brine. The organic layer was dried (MgSO4) and concentrated. The residue was purified by column chromatography to provide the title compound (300 mg, 74%, er=97:3). MS (ESI+): mass calcd. for C26H25BrFNO2, 482.4; m/z found, 483.4 [M+H]+. 1H NMR (400 MHz, CDCl3): 7.59-7.54 (m, 2H), 7.41-7.20 (m, 7H), 7.02-6.91 (m, 2H), 6.72 (d, J=6.5 Hz, 2H), 4.11-4.07 (m, 1H), 3.19-3.08 (m, 2H), 1.45 (s, 9H).

후처리

  1. stirringstirred at −55° C. overnight
  2. temperaturewarmed to rt
  3. washwashed with water and brine
  4. dry with materialThe organic layer was dried (MgSO4)
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography

출처 및 근거

ORD 기록
ord-d339b6c68792456188fd2781964ea0c5
출처 데이터셋
uspto-grants-2010_12
특허 번호
US07855292B2

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