Cesium carbonate → HCID 86674749, compound

HRID 927428Notes

Reaction equation

HRID 927428 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][N:6]=1)=[O:4].[CH:12]1(B(O)O)[CH2:14][CH2:13]1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([CH:12]2[CH2:14][CH2:13]2)=[CH:7][N:6]=1)=[O:4]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2760897Cyclopropylboronic acidHCID 7016458Methyl 5-bromopyridine-2-carboxylate

Product 1

HCID 86674749HCID 86674749, compoundYield 45.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

5-Bromo-pyridine-2-carboxylic acid methyl ester (CAN 29682-15-3, 2.16 g, 0.01 mol), cyclopropylboronic acid (CAN 411235-57-9, 0.9 g, 0.01 mol), tris(dibenzylideneacetone)dipalladium (CAN 52409-22-0, 0.2 g), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (CAN 161265-03-8, 0.3 g) and cesium carbonate (CAN 534-17-8, 3.3 g, 0.01 mol) was added into 1,4-dioxane (40 mL). The mixture was stirred for 12 h at 110° C. under nitrogen atmosphere. Subsequently, the mixture was filtered and concentrated. The residue was poured into water (20 mL) and extracted with ethyl acetate (3×20 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated to give crude product. The crude product was purified by a flash column chromatography (silica gel, 50 g, eluting with 20% ethyl acetate in petroleum ether) to give product (0.8 g, 45%); MS (EI): m/e 178.1 [M+H]+.

Workup

  1. filtrationSubsequently, the mixture was filtered
  2. concentrationconcentrated
  3. additionThe residue was poured into water (20 mL)
  4. extractionextracted with ethyl acetate (3×20 mL)
  5. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customto give crude product
  8. customThe crude product was purified by a flash column chromatography (silica gel, 50 g, eluting with 20% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-1e1810461ecb42a39637ba3dd44edbfc
Source dataset
uspto-grants-2016_03
Patent number
US09290451B2

Reaction notes

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