Potassium Carbonate → Methyl 4-bromo-3-methylthiophene-2-carboxylate

HRID 2392272Notes

Reaction equation

HRID 2392272 reaction equation
[Br:1][C:2]1[C:3](OS(C(F)(F)F)(=O)=O)=[C:4]([C:7]([O:9][CH3:10])=[O:8])[S:5][CH:6]=1.[C:19]([O-])([O-])=O.[K+].[K+].CB(O)O>O1CCOCC1.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>[Br:1][C:2]1[C:3]([CH3:19])=[C:4]([C:7]([O:9][CH3:10])=[O:8])[S:5][CH:6]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 139377Methylboronic AcidHCID 56933717Methyl 4-bromo-3-{[(trifluoromethyl)sulfonyl]oxy}-2-thiophenecarboxylate

Product 1

HCID 59212115Methyl 4-bromo-3-methylthiophene-2-carboxylateYield 84%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
70 °C

Procedure

To a solution of methyl 4-bromo-3-{[(trifluoromethyl)sulfonyl]oxy}-2-thiophenecarboxylate (825 mg, 2.25 mmol) in dioxane/H2O (5 mL/1 mL) was added K2CO3 (930 mg, 6.75 mmol), tetrakistriphenylphosphine Pd(0) (260 mg, 0.22 mmol), and methylboronic acid (175 mg, 2.91 mmol). The reaction mixture was heated to 70° C. in a sealed tube for 12 h. The reaction solution was concentrated under vacuum and purified on silica gel (hexanes/EtOAc, 9:1) to give the title compound (441 mg, 84%) as a brown solid: LC-MS (ES) m/z 236 (M+H)+.

Workup

  1. concentrationThe reaction solution was concentrated under vacuum
  2. custompurified on silica gel (hexanes/EtOAc, 9:1)

Sources & evidence

ORD record
ord-ed7261683e3a445eb1d7bf245bb94a3b
Source dataset
uspto-grants-2012_09
Patent number
US08273782B2

Reaction notes

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