Ethyl Acetate → 5-(5-Chloro-2-methylbenzoxazol-6-yl)-2-pyridylamine

HRID 1036082Notes

Reaction equation

HRID 1036082 reaction equation
Br[C:2]1[C:11]([Cl:12])=[CH:10][C:5]2[N:6]=[C:7]([CH3:9])[O:8][C:4]=2[CH:3]=1.[NH2:13][C:14]1[CH:19]=[CH:18][C:17](B2OC(C)(C)C(C)(C)O2)=[CH:16][N:15]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].CC(=O)OCC>C(#N)C.O1CCOCC1.O>[Cl:12][C:11]1[C:2]([C:17]2[CH:18]=[CH:19][C:14]([NH2:13])=[N:15][CH:16]=2)=[CH:3][C:4]2[O:8][C:7]([CH3:9])=[N:6][C:5]=2[CH:10]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 62657Potassium Phosphate, TribasicHCID 27565555-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amineHCID 584874386-Bromo-5-chloro-2-methylbenzoxazole

Product 1

HCID 584870245-(5-Chloro-2-methylbenzoxazol-6-yl)-2-pyridylamineYield 60.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 6-bromo-5-chloro-2-methylbenzoxazole (35) (123 mg, 0.5 mmol), 2-aminopyridine-5-boronic acid pinacol ester (11) (130 mg, 0.6 mmol), Bis(dicyclohexyl(4-dimethylaminophenyl)phosphine)dichloropalladium (II) (35 mg) and K3PO4 (106 mg, 0.5 mmol) in 1 ml ACN, 1 ml dioxane, 0.25 ml H2O was bubbled with argon before heated at 85° C. for 6 h. After cooling down to r.t., the reaction mixture was taken up in EA, washed with aq. NaHCO3 and brine, dried over Na2SO4, concentrated to dryness. The resulting red solid was dissolved in DCM and subjected to silica gel column purification using 0-100% B (A: hexane; B: EA) to furnish 78 mg 36 as off-white solid (yield: 60%)

Workup

  1. customwas bubbled with argon
  2. temperatureAfter cooling down to r.t.
  3. washwashed with aq. NaHCO3 and brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated to dryness
  6. dissolutionThe resulting red solid was dissolved in DCM
  7. customsubjected to silica gel column purification

Sources & evidence

ORD record
ord-3c5b9ac5915c4d24bd53570aa74c30dd
Source dataset
uspto-grants-2013_10
Patent number
US08546403B2

Reaction notes

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