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

HRID 2265307ノート

反応式

HRID 2265307 の反応式
[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]

参加物

7

反応物 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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
-55 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-d339b6c68792456188fd2781964ea0c5
出典データセット
uspto-grants-2010_12
特許番号
US07855292B2

反応ノート

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