Cesium carbonate → Ethyl 6'-{[(ethylamino)carbonyl]amino}-5''-fluoro-3,3':4',3''-terpyridine-5-carboxylate

HRID 2243033Notes

Reaction equation

HRID 2243033 reaction equation
Br[C:2]1[C:3]([C:14]2[CH:15]=[N:16][CH:17]=[C:18]([F:20])[CH:19]=2)=[CH:4][C:5]([NH:8][C:9]([NH:11][CH2:12][CH3:13])=[O:10])=[N:6][CH:7]=1.CC1(C)C(C)(C)OB([C:29]2[CH:30]=[N:31][CH:32]=[C:33]([CH:39]=2)[C:34]([O:36][CH2:37][CH3:38])=[O:35])O1.C(=O)([O-])[O-].[Cs+].[Cs+]>>[CH2:12]([NH:11][C:9]([NH:8][C:5]1[N:6]=[CH:7][C:2]([C:29]2[CH:30]=[N:31][CH:32]=[C:33]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH:39]=2)=[C:3]([C:14]2[CH:15]=[N:16][CH:17]=[C:18]([F:20])[CH:19]=2)[CH:4]=1)=[O:10])[CH3:13]

Participants

4

Reactant 3

HCID 10796Cesium carbonateHCID 3816953Ethyl 5-(tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-3-carboxylateHCID 59208332N-(5'-bromo-5-fluoro-3,4'-bipyridin-2'-yl)-N'-ethylurea2×

Product 1

HCID 59208334Ethyl 6'-{[(ethylamino)carbonyl]amino}-5''-fluoro-3,3':4',3''-terpyridine-5-carboxylateYield 46.4%

Conditions

Temperature
100 °C

Procedure

N-(5′-bromo-5-fluoro-3,4′-bipyridin-2′-yl)-N′-ethylurea (Intermediate 30, 0.34 g, 1.00 mmol), ethyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nicotinate (Oakwood Products, Inc., Cat. #021607) (0.306 g, 1.10 mmol), tetrakis triphenyl phosphine palladium (0.058 g, 0.05 mmol), and cesium carbonate (0.359 g, 1.10 mmol) were added to a microwave vial and degassed with nitrogen. A solution of 1,4-dioxane:water (4:1, 10 mL) was added to the solution and the reaction mixture was heated to 100° C. for 30 minutes. The reaction mixture was partitioned between water and ethyl acetate, and the organic layer was washed with saturated sodium bicarbonate solution, water, and brine, then dried over magnesium sulfate. The solvent was removed and the residue was purified by silica gel chromatography, eluting with (0-100% EtOAc/hexanes) to give the title compound as a white solid (190 mg). MS (ESP): 410 (MH+) for C21H20FN5O3;

Workup

  1. customdegassed with nitrogen
  2. additionA solution of 1,4-dioxane:water (4:1, 10 mL) was added to the solution
  3. customThe reaction mixture was partitioned between water and ethyl acetate
  4. washthe organic layer was washed with saturated sodium bicarbonate solution, water, and brine
  5. dry with materialdried over magnesium sulfate
  6. customThe solvent was removed
  7. customthe residue was purified by silica gel chromatography
  8. washeluting with (0-100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-2b94de32c4c24cbea31bde6943355beb
Source dataset
uspto-grants-2010_03
Patent number
US07674801B2

Reaction notes

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