反应详情

Pd(acac)2 (6.1 mg, 0.02 mmol, 0.5 mol %) and Xantphos (23.2 mg, 0.04 mmol, 1 mol o) are introduced into a flared flask provided with coolant. 4-bromophenylmethylsulfone of formula (III, X═Br) (1.17 g, 5 mmol), acetylpicoline of formula (II) (541 mg, 4 mmol) and K3PO4 (2.55 g, 12.0 mmol, 3 eq) are added thereto. Once the argon atmosphere has been stabilized with vacuum-argon cycles, anhydrous and degassed NMP (15 ml) is added with a syringe. The mixture is then kept stirred under stirring in an argon atmosphere for 18 h at 100° C. The conversion is quantitative. The reaction mixture is diluted with a saturated solution of NaHCO3 (50 mL) and extracted with AcOEt (4×50 mL). The combined organic phases were washed with an aqueous solution saturated with NaHCO3 (30 mL), anhydrified on MgSO4 and concentrated in a vacuum. The residue was purified by silica gel chromatography using AcOEt/cyclohexane as eluent in a gradient from 5:5 to 10:0. 1.05 g product were obtained, for a molar yield of 91% as a white crystalline solid.

1. customprovided with coolant
2. customanhydrous and degassed NMP (15 ml)
3. additionis added with a syringe
4. stirringunder stirring in an argon atmosphere for 18 h at 100° C
5. additionThe reaction mixture is diluted with a saturated solution of NaHCO3 (50 mL)
6. extractionextracted with AcOEt (4×50 mL)
7. washThe combined organic phases were washed with an aqueous solution saturated with NaHCO3 (30 mL)
8. concentrationconcentrated in a vacuum
9. customThe residue was purified by silica gel chromatography