Tri-o-tolylphosphine → HCID 22221607, compound

HRID 1794501Notes

Reaction equation

HRID 1794501 reaction equation
Br[C:2]1[C:10]2[O:9][C:8]([C:11]3[CH:16]=[CH:15][C:14]([O:17][Si](C(C)(C)C)(C)C)=[CH:13][CH:12]=3)=[CH:7][C:6]=2[CH:5]=[C:4]([O:25][Si](C(C)(C)C)(C)C)[CH:3]=1.[CH2:33]([Sn](CCCC)(CCCC)C=C)[CH2:34]CC.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(C1C2OC=CC=2C=CC=1)=C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1(C)C(C)=CC=CC=1.C1COCC1.C(OCC)C>[OH:17][C:14]1[CH:13]=[CH:12][C:11]([C:8]2[O:9][C:10]3[C:2]([CH:33]=[CH2:34])=[CH:3][C:4]([OH:25])=[CH:5][C:6]=3[CH:7]=2)=[CH:16][CH:15]=1

Participants

9

Reactant 5

HCID 80271Tri-o-tolylphosphineHCID 81998TributylvinyltinHCID 2724141Tetrabutylammonium FluorideHCID 22221616HCID 22221616, compoundHCID 86589548HCID 86589548, compound

Product 1

HCID 22221607HCID 22221607, compoundYield 83.7%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 7237O-XyleneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
130 °C

Procedure

To a solution of 66 (0.48 g, 0.9 mmol) in xylene was added tributyl vinyl tin (0.28 g, 0.9 mmol) and tri-(o-tolyl)phosphine (0.055 g, 0.18 mmol). This mixture was purged with nitrogen for 15 minutes. Then palladium (II) chloride was added and there action was heated at 130° C. for 2 hours. The reaction was filtered and the solvent removed in vacuo. The residue was used in the next step without further purification. To a solution of 5-(tert-butyl-dimethyl-silanyloxy)-2-[4-tert-butyl-dimethyl-silanyloxy)-phenyl]-7-vinyl-benzofuran (0.4 g, 0.9 mmol) in THF (10 mL) was added 1.0M tetrabutyl ammonium fluoride (1.8 mL, 1.8 mmol) and the reaction mixture was stirred at room temperature 20 minutes. The reaction was diluted with ethyl ether and washed twice with water. The organic layer was dried over MgSO4 and the solvent removed in vacuo. The product was purified via flash chromatography, eluting with 50% ethyl acetate in hexane, to give 0.19 g of 2-(4-hydroxy-phenyl)-7-vinyl-benzofuran-5-ol 67: Mp=182–184° C.; 1H NMR (DMSO-d6) δ 9.86 (s, 1 H), 9.20 (s, 1 H), 7.73 (d, 2 H, J=8.6 HZ), 7.06 (s, 1 H), 6.89 (d, 2 H, J=8.8 Hz), 6.92 (dd, 1 H, J=16.7 Hz, 11.3 Hz), 6.84 (d, 1 H, J=2.3 Hz), 6.76 (d, 1 H, J=2.3 Hz), 6.21 (dd, 1 H, J=17.8 Hz, 1.2 Hz), 5.54 (dd, 1 H, J=11.3 Hz, 1.2 Hz); MS 253 (M+H)+.

Workup

  1. customThis mixture was purged with nitrogen for 15 minutes
  2. additionThen palladium (II) chloride was added
  3. filtrationThe reaction was filtered
  4. customthe solvent removed in vacuo
  5. customThe residue was used in the next step without further purification
  6. washwashed twice with water
  7. dry with materialThe organic layer was dried over MgSO4
  8. customthe solvent removed in vacuo
  9. customThe product was purified via flash chromatography
  10. washeluting with 50% ethyl acetate in hexane

Sources & evidence

ORD record
ord-4c3ac945802948c9b4a37cc8049aa92d
Source dataset
uspto-grants-2006_04
Patent number
US07022733B2

Reaction notes

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