Sodium Carbonate → 2-t-Butyldimethylsilyl-3-(t-butyldimethylsilyloxymethylene)-6-methoxy-benzofuran

HRID 1020469노트

반응식

HRID 1020469 반응식
I[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=1[OH:10].[Si:11]([C:18]#[C:19][CH2:20][O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].[Cl-].[Li+].C(=O)([O-])[O-].[Na+].[Na+]>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Si:11]([CH:18]1[C:19](=[CH:20][O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:23])[CH3:24])[C:2]2[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][C:3]=2[O:10]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12]

참가 물질

7

반응물 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 10968062Tert-butyl(3-(tert-butyldimethylsilyl)prop-2-ynyloxy)-dimethylsilaneHCID 114140152-Iodo-5-methoxyphenol

생성물 1

HCID 672878412-t-Butyldimethylsilyl-3-(t-butyldimethylsilyloxymethylene)-6-methoxy-benzofuran수율 87%

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 6228Dimethylformamide용매

실험 절차

A suspension of 2-iodo-5-methoxyphenol (1.1 g, 4.41 mmol), 1-(tert-butyldimethylsilyl)-3-(tert-butyldimethylsilyloxy)propyne (1.5 g, 5.28 mmol), lithium chloride (189 mg, 4.45 mmol) and sodium carbonate (2.34 g, 22.08 mmol) in dry dimethylformamide (5 mL) at 100° C. was deoxygenated 4 times by evacuation and backfilling with nitrogen. Palladium acetate (135 mg, 0.60 mmol) was added and the reaction vessel was degassed twice with nitrogen. The reaction mixture was then stirred at this temperature for 4 hours (monitored by tlc) and the solvent was removed by distillation under vacuum. The residue was dissolved in ethyl acetate (75 mL), stirred well, filtered and treated with triethylamine (5 mL). The solution was concentrated onto silica gel (10 g) and purified by flash chromatography (silica gel, eluent=hexane/diethyl ether/triethylamine; 95:5:1%) to give the title compound as a yellow oil (1.09 g, 87%); 1H NMR (300 MHz, CDCl3) δ 7.52 (d, 1H, J=8.57 Hz), 6.97 (d, 1H, J=2.15 Hz), 6.83 (dd, 1H, J=8.54, 2.18 Hz), 4.81 (s, 2H, CH2), 3.83 (s, 3H, OMe), 0.93 (s, 9H), 0.91 (s, 9H), 0.34 (s, 6H), 0.11 (s, 6H).

후처리

  1. customwas deoxygenated 4 times by evacuation and backfilling with nitrogen
  2. customthe reaction vessel was degassed twice with nitrogen
  3. customthe solvent was removed by distillation under vacuum
  4. dissolutionThe residue was dissolved in ethyl acetate (75 mL)
  5. stirringstirred well
  6. filtrationfiltered
  7. additiontreated with triethylamine (5 mL)
  8. concentrationThe solution was concentrated onto silica gel (10 g)
  9. custompurified by flash chromatography (silica gel, eluent=hexane/diethyl ether/triethylamine; 95:5:1%)

출처 및 근거

ORD 기록
ord-7ce0cd4c04e447379eb967cf2f4ebcc4
출처 데이터셋
uspto-grants-2014_05
특허 번호
US08716335B2

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