Stage #1: With bis-triphenylphosphine-palladium(II) chloride; potassium acetate In tetrahydrofuran at 20℃; for 0.08 h; Inert atmosphere
Stage #2: at 80℃; for 24.00 h; Inert atmosphere
|4-Bromodibenzofuran 10.0g (38.1 mmol) was dissolved in 300ml tetrahydrofuran and then, Bis (triphenylphosphine) palladium (II) dichloride 1.3g (1.9 mmol) was added at the room temperature was stirred for about 5 minutes dongan it. Thereafter, Bis (pinacolato) diboron 14.5g (57.2 mmol) and Potassium acetate 11.2g (114.3 mmol) and the mixture was heated under reflux for a day at 80 . When the reaction is complete, the extract was added to 200ml of ethyl acetate, and distilled under reduced pressure the organic layer was dried with magnesium sulfate. Purification of the separation results obtained therefrom by column chromatography to give Intermediate 12-3 about 10.0g (34.3 mmol, 90percent yield). The resulting compound was confirmed by LC-MS.
||With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide at 90℃;
||Sub-1-I-1 (15.76 g, 63.78 mmol) was dissolved in DMF (320 ml) into a round bottom flask,Bis (pinacolato) diboron (17.82 g, 70.16 mmol), Pd (dppf) Cl2 (1.56 g, 1.91 mmol) and KOAc (18.78 g, 191.35 mmol) were added and stirred at 90 ° C.When the reaction was complete, DMF was removed by distillation and extracted with CH2Cl2 and water.The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to give 15.38 g of the product (Yield: 82percent).
||With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide
||Sub 14-1 (15.76 g, 63.78 mmol) was added into a round bottom flask, then, dissolved in DMF (320 ml). After adding l3is(pinacolato)diboron (17.82 g, 70.16 mmol), Pd(dppCl2 (1.56 g, 1.91 mmol), KOAc (18.78 g, 191.35 mmol), stirring at 90 D was followed. When the reaction was completed, DMF was removed by distillation, and then extracting with CH2C12 and water was followed. The organic layer was dried with Mg504 and concentrated. Then, the concentrate was passed through silica gel colunm, then recrystallized to obtain 15.38 g (yield: 82percent) of the product.