Triphenylphosphine → HCID 86599491, compound

HRID 855114Notes

Reaction equation

HRID 855114 reaction equation
I[C:2]1[CH:3]=[C:4]([O:21][C:22]([F:25])([F:24])[F:23])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:15])([F:14])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2.[C:26]1(B(O)O)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1.O.[Cl-].[Na+].O.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCO>[C:26]1([C:2]2[CH:3]=[C:4]([O:21][C:22]([F:24])([F:23])[F:25])[CH:5]=[C:6]3[C:11]=2[O:10][CH:9]([C:12]([F:14])([F:15])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]3)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

11

Reactant 4

HCID 11776TriphenylphosphineHCID 66827Phenylboronic Acid2×HCID 516892Sodium Bicarbonate2×HCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 86599491HCID 86599491, compound

Reagents, catalysts & solvents 6

HCID 167845palladium(II) acetateCatalystHCID 178418397HCID 178418397, compoundCatalyst2×HCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture of ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 21a, Step 2 (0.500 g, 1.04 mmole), phenylboronic acid (133 mg, 1.09 mmole), Pd(OAc)2 (7.00 mg, 0.031 mmole), triphenyl phosphine (24.4 mg, 0.093 mmole), and NaHCO3 (132 mg, 1.25 mmole) in toluene (25 mL) and H2O (5 mL) was stirred at room temperature for 21 hrs and was then refluxed for 1 h. Pd(PPh3)4 (120 mg, 0.104 mmole) was added and the mixture was refluxed for 1.5 hrs. LCMS indicated that the product was increased slightly. Additional Pd(PPh3)4 (120 mg, 0.104 mmole), NaHCO3 (132 mg, 1.25 mmole) and phenylboronic acid (133 mg, 1.09 mmole) and EtOH (10 mL) to above mixture and the mixture was refluxed overnight. After cooling, the mixture was then poured into brine (100 mL) and extracted with EtOAc (100 mL). The EtOAc layer was separated, dried over MgSO4 and filtered. The crude product was purified by silica chromatography (0-10% EtOAc—hexanes) to give 336 mg (85%, yield) of the product as an off-white solid: EIHRMS m/z 432.0807 (M+, C20H14F6O4, Calc'd 432.0796).

Workup

  1. temperaturewas then refluxed for 1 h
  2. temperaturethe mixture was refluxed for 1.5 hrs
  3. temperaturewas increased slightly
  4. temperatureAfter cooling
  5. extractionextracted with EtOAc (100 mL)
  6. customThe EtOAc layer was separated
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. customThe crude product was purified by silica chromatography (0-10% EtOAc—hexanes)
  10. customto give

Sources & evidence

ORD record
ord-d69d5088b279418bb0e7d58715b82d7f
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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