Formic Acid → Methyl thieno[2,3-b]pyridine-5-carboxylate

HRID 2080023Notes

Reaction equation

HRID 2080023 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]2[CH:21]=[CH:20][S:19][C:8]2=[N:9][C:10]=1OS(C(F)(F)F)(=O)=O)=[O:4].C(O)=O.C(N(CC)C(C)C)(C)C.O>CN1CCCC1=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>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]2[CH:21]=[CH:20][S:19][C:8]2=[N:9][CH:10]=1)=[O:4]

Participants

8

Reactant 4

HCID 284Formic AcidHCID 962WaterHCID 81531DiisopropylethylamineHCID 58875349HCID 58875349, compound

Product 1

HCID 21817753Methyl thieno[2,3-b]pyridine-5-carboxylate

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
100 °C

Procedure

6-Trifluoromethanesulfonyloxy-thieno[2,3-b]pyridine-5-carboxylic acid methyl ester described in Preparation Example T-9 (10 mg, 29 μmol), tetrakis(triphenylphosphine)palladium(0) (3.4 mg, 2.9 μmol), formic acid (1.7 μl, 44 μmol) and N,N-diisopropylethylamine (15 μl, 87 μmol) were dissolved in 1-methyl-2-pyrrolidone (0.5 mL), and the mixture was stirred for 1.5 hours at 100° C. The reaction mixture was cooled to room temperature, water and ethyl acetate were added, the organic layer was partitioned, the organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated in vacuo, the residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=5:1), and the title compound (7 mg, quantitatively) was obtained as a white solid.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customthe organic layer was partitioned
  3. washthe organic layer was washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customThe solvent was evaporated in vacuo
  6. customthe residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=5:1)

Sources & evidence

ORD record
ord-4b085073c61944209e6c2c77853628f9
Source dataset
uspto-grants-2011_04
Patent number
US07932272B2

Reaction notes

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