Water → HCID 66990886, compound

HRID 444627Notes

Reaction equation

HRID 444627 reaction equation
[CH2:1]([O:8][C:9]1[C:14](OC)=[CH:13][C:12](B(O)O)=[C:11]([O:20][CH3:21])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:22][O:23][C:24](=[O:42])[C:25]1[CH:30]=[C:29]([C:31](=[O:33])[CH3:32])[CH:28]=[CH:27][C:26]=1OS(C(F)(F)F)(=O)=O.C([O-])([O-])=O.[K+].[K+].O>[Cl-].[Na+].O.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.C(OCC)(=O)C>[CH3:22][O:23][C:24]([C:25]1[C:26]([C:12]2[CH:13]=[CH:14][C:9]([O:8][CH2:1][C:2]3[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=3)=[CH:10][C:11]=2[O:20][CH3:21])=[CH:27][CH:28]=[C:29]([C:31](=[O:33])[CH3:32])[CH:30]=1)=[O:42]

Participants

8

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 10935085B-[2,5-Dimethoxy-4-(phenylmethoxy)phenyl]boronic acidHCID 11438780methyl 5-acetyl-2-{[(trifluoromethyl)-sulfonyl]oxy}benzoate

Product 1

HCID 66990886HCID 66990886, compoundYield 115.6%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

4-Benzyloxy-2,5-dimethoxyphenylboronic acid 5b (4.15 g, 14.4 mmol), 5-Acetyl-2-trifluoromethanesulfonyloxy-benzoic acid methyl ester 6 (4.69 g, 14.4 mmol) and K2CO3 (3.98 g, 28.8 mmol) were added and the flask was flushed with Ar. Absolute ethanol (83 mL) and DME (94 mL) were added followed by Pd (PPh3)4 (0.87 g, 0.785 mmol) and the reaction mixture refluxed for 4 h. After cooling, water (100 ml), ethyl acetate (100 mL) and brine (50 mL) were added. The organic layer was washed with brine (2×50 mL) and the combined aqueous fraction was back extracted with ethyl acetate. The combined organic fraction was dried, concentrated and recrystallized from ethyl acetate/hexanes to give 6.5 g (99%) of 7b as a yellow solid. 1H-NMR (400 MHz, CDCl3) dH 2.65 (3H, s, COCH3), 3.58 (3H, s, OCH3), 3.68 (3H, s, OCH3), 3.88 (3H, s, OCH3), 5.21 (21H, s, CH2Ph), 6.55 (1H, s, ArH), 6.86 (1H, s, ArH), 7.30-7.48 (6H, m, ArH+CH2Ph), 8.10 (1H, d, ArH),8.37(1H,s,ArH),

Workup

  1. customthe flask was flushed with Ar
  2. additionAbsolute ethanol (83 mL) and DME (94 mL) were added
  3. temperaturethe reaction mixture refluxed for 4 h
  4. temperatureAfter cooling
  5. washThe organic layer was washed with brine (2×50 mL)
  6. extractionthe combined aqueous fraction was back extracted with ethyl acetate
  7. customThe combined organic fraction was dried
  8. concentrationconcentrated
  9. customrecrystallized from ethyl acetate/hexanes

Sources & evidence

ORD record
ord-d562becfaf2a4522a0484b22c6bddc18
Source dataset
uspto-grants-2013_07
Patent number
US08475776B2

Reaction notes

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