1,2-Dimethoxyethane → HCID 118046042, compound

HRID 595821Notes

Reaction equation

HRID 595821 reaction equation
FC(F)(F)S(O[C:7]1[CH2:11][CH2:10][S:9][CH:8]=1)(=O)=O.CC1(C)C(C)(C)OB([C:22]2[CH:23]=[CH:24][C:25]([NH2:28])=[N:26][CH:27]=2)O1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].COCCOC>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[S:9]1[CH2:10][CH2:11][C:7]([C:22]2[CH:23]=[CH:24][C:25]([NH2:28])=[N:26][CH:27]=2)=[CH:8]1

Participants

7

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 62657Potassium Phosphate, TribasicHCID 27565555-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amineHCID 118045828HCID 118045828, compound

Product 1

HCID 118046042HCID 118046042, compound

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To a vial was charged with all reagents: 4,5-dihydrothiophen-3-yl trifluoromethanesulfonate (900 mg, 3.84 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amine(1.69 g, 7.69 mmol), K3PO4 (2.45 g, 11.5 mmol), and PdCl2(dppf)-CH2Cl2 adduct (314 mg, 0.384 mmol) and DME (16 mL), and the mixture was purged with Argon, then sealed and heated at 90° C. via external oil bath overnight. The reaction mixture was cooled down to room temperature, and the precipitates in the reaction mixture was removed by filtration, and the filtrate was concentrated under reduced pressure and a black residue was obtained as crude product. The crude product was dissolved in EtOAc (30 mL), washed with water (20 mL), and the slug between the two layers was removed by filtration. The EtOAc layer was collected, stripped with 1N HCl (2×20 mL) and the aqueous layers were combined, scrubbed with EtOAc (20 mL), basified with aqueous NaOH (3 g in 10 mL water), extracted with EtOAc (2×30 mL), and the obtained EtOAc extracts were combined, washed with brine (30 mL), dried (Na2SO4), concentrated and desired product was obtained as light color solid. LCMS (m/z): 179.0 (MH+), 0.41, 0.43 min (for regioisomers).

Workup

  1. additionTo a vial was charged with all reagents
  2. customsealed
  3. temperatureThe reaction mixture was cooled down to room temperature
  4. customthe precipitates in the reaction mixture
  5. customwas removed by filtration
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. customa black residue was obtained as crude product
  8. washwashed with water (20 mL)
  9. customthe slug between the two layers was removed by filtration
  10. customThe EtOAc layer was collected
  11. extractionextracted with EtOAc (2×30 mL)
  12. washwashed with brine (30 mL)
  13. dry with materialdried (Na2SO4)
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-614b67c2986946d0bd6c984f5cab7591
Source dataset
uspto-grants-2016_01
Patent number
US09242996B2

Reaction notes

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