Tri-o-tolylphosphine → (E)-5-(4-(benzyloxy)styryl)-N-(4-(difluoromethoxy)phenyl)pyrimidin-2-amine

HRID 77489

反応式

HRID 77489 の反応式
[F:1][CH:2]([F:19])[O:3][C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:11]2[N:16]=[CH:15][C:14]([CH:17]=[CH2:18])=[CH:13][N:12]=2)=[CH:6][CH:5]=1.[CH2:20]([O:27][C:28]1[CH:33]=[CH:32][C:31](I)=[CH:30][CH:29]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C(Cl)(Cl)Cl.[Pd].[Pd]>[CH2:20]([O:27][C:28]1[CH:33]=[CH:32][C:31](/[CH:18]=[CH:17]/[C:14]2[CH:15]=[N:16][C:11]([NH:10][C:7]3[CH:8]=[CH:9][C:4]([O:3][CH:2]([F:1])[F:19])=[CH:5][CH:6]=3)=[N:12][CH:13]=2)=[CH:30][CH:29]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

参加物

6

反応物 3

HCID 80271Tri-o-tolylphosphineHCID 5196711-(Benzyloxy)-4-iodobenzeneHCID 86679783N-(4-(difluoromethoxy)phenyl)-5-vinylpyrimidin-2-amine

生成物 1

HCID 86679782(E)-5-(4-(benzyloxy)styryl)-N-(4-(difluoromethoxy)phenyl)pyrimidin-2-amine収率 70%

試薬・触媒・溶媒 2

HCID 11029508Palladium, tris[mu-[(1,2-eta:4,5-eta)-(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one]]di-, compd. with trichloromethane (1:1)触媒HCID 6342Acetonitrile溶媒

反応条件

温度
90 °C

実験手順

To a solution of N-(4-(difluoromethoxy)phenyl)-5-vinylpyrimidin-2-amine (0.102 g, 0.387 mmol) in ACN (3 mL) were added 1-(benzyloxy)-4-iodobenzene (0.1 g, 0.322 mmol), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (0.033 g, 0.032 mmol), tri-o-tolylphosphine (0.039 g, 0.129 mmol), and TEA (0.135 mL, 0.967 mmol). The reaction mixture was flushed with N2 and heated at 90° C. overnight. Solvent was evaporated, and the residue was dissolved in ethyl acetate, filtered through celite and concentrated. The crude product was purified by flash chromatography on silica gel using 30% ethyl acetate in hexanes to give (E)-5-(4-(benzyloxy)styryl)-N-(4-(difluoromethoxy)phenyl)pyrimidin-2-amine (0.1 g, 70%). 1H NMR (400 MHz, DMSO-d6) δ ppm 5.14 (s, 2H), 6.93-7.30 (m, 7H), 7.34-7.52 (m, 2H), 7.78-7.80 (m, 2H), 8.71 (s, 2H), 9.82 (s, 1H). LCMS: RT 1.18 min, (M+H)+446.6.

後処理

  1. customThe reaction mixture was flushed with N2
  2. customSolvent was evaporated
  3. dissolutionthe residue was dissolved in ethyl acetate
  4. filtrationfiltered through celite
  5. concentrationconcentrated
  6. customThe crude product was purified by flash chromatography on silica gel using 30% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-dce1644f735941578e3238b2fd93288c
出典データセット
uspto-grants-2014_09
特許番号
US08841301B2

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