Potassium Carbonate → tert-butyl 4-(3-bromophenyl)-3,6-dihydropyridine-1(2H)-carboxylate

HRID 2354953ノート

反応式

HRID 2354953 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11](B2OC(C)(C)C(C)(C)O2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[Br:23][C:24]1[CH:29]=[CH:28][CH:27]=[C:26](I)[CH:25]=1.C([O-])([O-])=O.[K+].[K+]>CN(C)C=O.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11]([C:26]2[CH:27]=[CH:28][CH:29]=[C:24]([Br:23])[CH:25]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 11561Benzene, 1-bromo-3-iodo-HCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylate

生成物 1

HCID 66836951tert-butyl 4-(3-bromophenyl)-3,6-dihydropyridine-1(2H)-carboxylate

試薬・触媒・溶媒 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

A stirred mixture of 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (prepared as described in Tetrahedron Letters 2000, 3705-3708; 6.52 g, 21.1 mmol), 1-bromo-3-iodobenzene (4.05 mL, 31.8 mmol), bis-(triphenyl-phosphine)-palladium(II) chloride (892 mg, 1.27 mmol), K2CO3 (8.7 g, 63 mmol) and 1,1′-bis(diphenylphosphino)ferrocene (704 mg, 1.27 mmol) in 120 mL dimethylformamide is heated at 80° C. under argon for 14 h. The mixture is cooled to RT, dimethylformamide is removed in vacuo. After addition of brine, the aqueous layer is extracted three times with CH2Cl2. The combined organic extracts are dried (Na2SO4) and evaporated in vacuo. Flash chromatography of the residue (SiO2, hexane/ethyl acetate) affords 4-(3-bromo-phenyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid t-butyl ester as a colourless viscous resin: MS 338.2/340.2 [M+H]+; retention time 8.01 min (HPLC, Nucleosil C18; 5→100% CH3CN in H2O within 8 min, then 100% CH3CN for 2 min).

後処理

  1. temperatureThe mixture is cooled to RT
  2. customdimethylformamide is removed in vacuo
  3. additionAfter addition of brine
  4. extractionthe aqueous layer is extracted three times with CH2Cl2
  5. dry with materialThe combined organic extracts are dried (Na2SO4)
  6. customevaporated in vacuo

出典と根拠

ORDレコード
ord-466e9202405a4bf1a046dae92c48ed45
出典データセット
uspto-grants-2010_07
特許番号
US07754727B2

反応ノート

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