Cesium carbonate → Benzyl 2-(4-(1-(tert-butyldimethylsilyloxy)cyclopropyl)-3-fluorophenyl)acrylate

HRID 1842902ノート

反応式

HRID 1842902 の反応式
[C:1]([Si:5]([O:8][C:9]1([C:12]2[CH:17]=[CH:16][C:15](B3OC(C)(C)C(C)(C)O3)=[CH:14][C:13]=2[F:27])[CH2:11][CH2:10]1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C([O-])([O-])=O.[Cs+].[Cs+].Br[C:35](=[CH2:46])[C:36]([O:38][CH2:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)=[O:37]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Si:5]([O:8][C:9]1([C:12]2[CH:17]=[CH:16][C:15]([C:35](=[CH2:46])[C:36]([O:38][CH2:39][C:40]3[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=3)=[O:37])=[CH:14][C:13]=2[F:27])[CH2:11][CH2:10]1)([C:1]([CH3:2])([CH3:4])[CH3:3])([CH3:7])[CH3:6]

参加物

6

反応物 3

HCID 10796Cesium carbonateHCID 13443472Benzyl 2-bromoprop-2-enoateHCID 70815542Tert-butyl(1-(2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropoxy)-dimethylsilane

生成物 1

HCID 86672144Benzyl 2-(4-(1-(tert-butyldimethylsilyloxy)cyclopropyl)-3-fluorophenyl)acrylate収率 37.2%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
95 °C

実験手順

To a stirred and degassed (degassed with Argon) suspension of tert-butyl(1-(2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropoxy)-dimethylsilane (10.23 g, 26.09 mmol, leg), Cs2CO3 (30.69 g, 78.27 mmol, 3 eq), and benzyl 2-bromoacrylate (9.59 g, 39.14 mmol, 1.5 eq) in DMF (100 mL) was added Pd(dppf)Cl2 (1.06 g, 1.305 mmol, 0.05 eq) and the mixture heated to 90-100° C. for 1 h. The reaction mixture was filtered through celite pad, diluted with water (100 mL) and extracted with ethyl acetate (250 mL). The ethyl acetate layer was washed with water (150 mL), brine (200 mL), dried (Na2SO4) and the solvent evaporated to get crude benzyl 2-(4-(1-(tert-butyldimethylsilyloxy)-cyclopropyl)-3-fluorophenyl)acrylate (4.14 g) as a yellow oil which was used for the next stage without purification (TLC system: EtOAc/PE (1:49), Rf: 0.5).

後処理

  1. customdegassed
  2. filtrationThe reaction mixture was filtered through celite pad
  3. additiondiluted with water (100 mL)
  4. extractionextracted with ethyl acetate (250 mL)
  5. washThe ethyl acetate layer was washed with water (150 mL), brine (200 mL)
  6. dry with materialdried (Na2SO4)
  7. customthe solvent evaporated

出典と根拠

ORDレコード
ord-edfea75450fa4f58a2b05c4761fbe125
出典データセット
uspto-grants-2015_02
特許番号
US08946204B2

反応ノート

読み込み中…