Propyne → 4-(Tert-butyl-diphenyl-silanyloxymethyl)-2-prop-1-ynyl-pyridine

HRID 216657

반응식

HRID 216657 반응식
[C:1]([SiH2:5][O:6][C:7]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:8]1[CH:13]=[CH:12][N:11]=[C:10](Cl)[CH:9]=1)([CH3:4])([CH3:3])[CH3:2].[C:27]1(P(C2C=CC=CC=2)C2C=CC=CC=2)[CH:32]=CC=C[CH:28]=1.C(NCC)C.C#CC.C([O-])(O)=O.[Na+]>[Cl-].[Cl-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd+2].[Cu]I.CN(C)C=O>[C:1]([SiH2:5][O:6][C:7]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:8]1[CH:13]=[CH:12][N:11]=[C:10]([C:28]#[C:27][CH3:32])[CH:9]=1)([CH3:4])([CH3:3])[CH3:2]

참가 물질

9

반응물 5

HCID 6335PropyneHCID 8021DiethylamineHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 1317297514-(Tert-butyl-diphenyl-silanyloxymethyl)-2-chloro-pyridine

생성물 1

HCID 1317297504-(Tert-butyl-diphenyl-silanyloxymethyl)-2-prop-1-ynyl-pyridine수율 104.4%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 84124Bis(triphenylphosphine)palladium chloride촉매HCID 6228Dimethylformamide용매

반응 조건

온도
120 °C

실험 절차

A reaction tube is charged under an atmosphere of argon with 4-(tert-butyl-diphenyl-silanyloxymethyl)-2-chloro-pyridine (9.47 g, 24.79 mmol), palladium(II)-bis(triphenylphosphine)-dichloride (1.78 g, 2.49 mmol, 0.1 equiv), copper(I) iodide (477 mg, 2.49 mmol, 0.1 equiv), and triphenylphosphine (3.94 g, 14.9 mmol, 0.6 equiv). The tube is degassed by alternating three times between vacuum and argon. Diethylamine (39 ml) and N,N-dimethylformamide (2.0 ml), and propyne (50% in THF, 10.1 g, 247 mmol, 10 equiv) are added under an argon atmosphere. The tube is sealed, and the reaction mixture is heated under microwave irradiation for 20 minutes at 120° C. After cooling, the reaction mixture is poured into a semi-concentrated aqueous solution of NaHCO3. After three extractions with EtOAc, the combined organic layers are washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. Purification via flash chromatography (gradient from hexane/EtOAc 100:0 to 50:50) affords the title compound (6.0 g, 63%). 1H NMR (400 MHz, d6-DMSO): δ=8.41 (d, J=5.0 Hz, 1H), 7.57-7.55 (m, 4H), 7.43-7.32 (m, 11H), 7.27 (d, J=5.0 Hz, 1H), 4.72 (s, 2H), 1.99 (s, 3H), 0.98 (s, 9H). MS (ES+): 386 (M+H)+.

후처리

  1. customThe tube is degassed
  2. customThe tube is sealed
  3. temperatureAfter cooling
  4. extractionAfter three extractions with EtOAc
  5. washthe combined organic layers are washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification via flash chromatography (gradient from hexane/EtOAc 100:0 to 50:50)

출처 및 근거

ORD 기록
ord-bc6e4e11056541b791e25ed4147f8dbd
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08193236B2

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