Toluene → HCID 68995354, compound

HRID 1182492Notes

Reaction equation

HRID 1182492 reaction equation
[S:1]1[CH:5]=[CH:4][C:3](B(O)O)=[CH:2]1.Br[C:10]1[CH:28]=[CH:27][C:13]([C:14]([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[O:15])=[CH:12][CH:11]=1.C1(C)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+]>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(O)C>[CH2:25]([O:24][C:22](=[O:23])[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][C:14](=[O:15])[C:13]1[CH:12]=[CH:11][C:10]([C:3]2[CH:4]=[CH:5][S:1][CH:2]=2)=[CH:28][CH:27]=1)[CH3:26]

Participants

7

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 581760Thiophene-3-boronic acidHCID 11024292ETHYL 8-(4-BROMOPHENYL)-8-OXOOCTANOATE

Product 1

HCID 68995354HCID 68995354, compoundYield 20.3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolvent

Procedure

To a mixture of 3-thiophene boronic acid (383 mg, 3 mmol) and bromoester 49d (1.03 g, 3 mmol) were added anhydrous toluene (30 mL) and ethanol (1.5 mL) (20:1, c=1.0M) followed by 2M K2CO3 aqueous solution (3 mL, 6 mmol). The reaction mixture was stirred under nitrogen for 30 minutes and then Pd(PPh3)4 (191 mg, 5 mol %, 0.16 mmol) was quickly added. After 24 hours of reflux, the mixture was cooled to room temperature, filtered through a pad of Celite and rinsed with ethyl acetate (50 mL). The organic solution was washed with brine (30 mL), dried (MgSO4), and concentrated. Purification by flash silica gel chromatography (10% methanol in dichloromethane) followed by crystallization from ethyl acetate afforded the corresponding ester 115 (210 mg, 20% yield) as a white solid.

Workup

  1. temperatureAfter 24 hours of reflux
  2. filtrationfiltered through a pad of Celite
  3. washrinsed with ethyl acetate (50 mL)
  4. washThe organic solution was washed with brine (30 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customPurification by flash silica gel chromatography (10% methanol in dichloromethane)
  8. customfollowed by crystallization from ethyl acetate

Sources & evidence

ORD record
ord-55a085e35a524582a56a440cf84f3c45
Source dataset
uspto-grants-2007_10
Patent number
US07288567B2

Reaction notes

Loading…