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

HRID 1809795노트

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HRID 1809795 반응식
[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]

참가 물질

6

반응물 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

생성물 1

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

시약·촉매·용매 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)촉매HCID 6228Dimethylformamide용매

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온도
80 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-9358ead3e5824935b75e00ab74418a2c
출처 데이터셋
uspto-grants-2013_01
특허 번호
US08362040B2

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