3-[(E)-丁-2-烯酰基]-1,3-恶唑烷-2-one

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a stream of nitrogen, a solution of 3-crotonoyl-1,3-oxazolidin-2-one (78 mg, 0.5 mmol), anisidine trifluoromethanesulfonate (205 mg, 0.75 mmol) and Pd((R)-binap)(μ-OH)]2(OTf)2 (4.6 mg, 0.0025 mmol) in tetrahydrofuran (0.5 mL) was stirred at room temperatures for 12 hours. When no starting material remained was observed, a saturated aqueous solution of ammonium chloride was added to quench the reaction, and the resulting mixture was extracted with ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective 3-[3-(4-methoxyphenylamino)butyryl]-1,3-oxazolidin-2-one (128 mg, 92% yield). The enantiomeric excess ratio was determined to be 98% e.e. by a liquid chromatography with an optical isomer separating column (column: AD-H). to quench the reaction the resulting mixture was extracted with ethyl acetate The organic layer was concentrated purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a stream of nitrogen, a solution of 3-crotonoyl-1,3-oxazolidin-2-one (776 mg, 5.0 mmol), anisidine trifluoromethanesulfonate (1.64 g, 6.0 mmol), anisidine (3.1 mg, 0.005 mmol) and Pd((R)-segphos)(H2O)2(OTf)2 (26.3 mg, 0.005 mmol) in tetrahydrofuran (5 ml) was stirred at room temperatures for 24 hours. When no starting material remained was noticed, a saturated aqueous solution of ammonium chloride was added to quench the reaction and the resulting mixture was extracted with ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography (hexane: ethyl acetate=1:1) to give the objective 3-[3-(4-methoxyphenylamino)butyryl]-1,3-oxazolidin-2-one (1.16 g, in a yield of 83%). The enantiomeric excess ratio was determined to be 97% e.e. by a liquid chromatography with an optical isomer separating column (column: AD-H). to quench the reaction the resulting mixture was extracted with ethyl acetate The organic layer was concentrated purified by a silica gel column chromatography (hexane: ethyl acetate=1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a stream of nitrogen, a solution of 3-crotonoyl-1,3-oxazolidin-2-one (776 mg, 5.0 mmol), anisidine trifluoromethanesulfonate (1.64 g, 6.0 mmol), anisidine (3.1 mg, 0.005 mmol) and Pd((R)-segphos)(H2O)2(OTf)2 (26.3 mg, 0.005 mmol) in tetrahydrofuran (5 ml) was stirred at room temperatures for 24 hours. When no starting material remained was noticed, a saturated aqueous solution of ammonium chloride was added to quench the reaction and the resulting mixture was extracted with ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography (hexane: ethyl acetate=1:1) to give the objective 3-[3-(4-methoxyphenylamino)butyryl]-1,3-oxazolidin-2-one (1.16 g, in a yield of 83%). The enantiomeric excess ratio was determined to be 97% e.e. by a liquid chromatography with an optical isomer separating column (column: AD-H). to quench the reaction the resulting mixture was extracted with ethyl acetate The organic layer was concentrated purified by a silica gel column chromatography (hexane: ethyl acetate=1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 3-crotonoyl-1,3-oxazolidin-2-one (47 mg, 0.3 mmol) and Pd((R)-binap)(H2O)2(OTf)2 (8.0 mg, 0.0075 mmol) in toluene (1.5 ml) in a stream of nitrogen was cooled to 0° C., and aniline (42 mg, 0.45 mmol) was added. To the solution was dropwise added trifluoromethanesulfonic acid (63 μL, 0.45 mmol), and the resulting mixture was stirred at room temperature for 24 hours. When no starting material was detected, a saturated aqueous solution of ammonium chloride was added to quench the reaction, and the resulting mixture was extracted with ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective 3-(3-phenylaminobutyryl)-oxazolidin-2-one (66 mg, 89% yield). The enantiomeric excess ratio was determined to be 94%. e.e. by a liquid chromatography with an optical isomer separating column (column: AD-H). to quench the reaction the resulting mixture was extracted with ethyl acetate The organic layer was concentrated purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of Pd((R)-binap)(OH2)2(OTf)2 (26.6 mg, 0.025 mmol) in toluene (3 ml) were added 3-crotonoyl-1,3-oxazolidin-2-one (155 mg, 1.0 mmol) and anisidine (148 mg, 1.2 mmol). After the resulting mixture was stirred at room temperature for 3 hours, the reaction solution was concentrated and purified by a silica gel column chromatography (hexane:ethyl acetate=4:1) to give the objective 3-[3-(4-methoxyphenylamino)butyryl]-1,3-oxazolidin-2-one (228 mg, 82% yield). the reaction solution was concentrated purified by a silica gel column chromatography (hexane:ethyl acetate=4:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of anisidine (55.4 mg, 0.45 mmol) in toluene (1.5 ml) was cooled to 0° C., and trifluoromethanesulfonic acid (40 μL, 0.45 mmol) was added dropwise. The mixture was stirred for 10 minutes, and to this solution were added Pd((R)-binap)(OH2)2(OTf)2 (8 mg, 0.00752 mmol) and 3-crotonoyl-1,3-oxazolidin-2-one (47 mg, 0.3 mmol). The ice-cooling bath was removed and the mixture was reacted at room temperature for 20 hours. A saturated aqueous solution of ammonium chloride was added to quench the reaction, and the reaction mixture was extracted with ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography (hexane:ethyl acetate=4:1) to give the objective 3-[3-(4-methoxyphenylamino)butyryl]-1,3-oxazolidin-2-one (66.5 mg, 96% yield). The enantiomeric excess was determined by a liquid chromatography with an optical isomer separating column (column: AD-H) to be 94% e.e. was removed the mixture was reacted at room temperature for 20 hours to quench the reaction the reaction mixture was extracted with ethyl acetate The organic layer was concentrated purified by a silica gel column chromatography (hexane:ethyl acetate=4:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of anisidine (55.4 mg, 0.45 mmol) in toluene (1.5 ml) was cooled to 0° C., and trifluoromethanesulfonic acid (40 μL, 0.45 mmol) was added dropwise. The mixture was stirred for 10 minutes, and to this solution were added Pd((R)-binap)(OH2)2(OTf)2 (8 mg, 0.00752 mmol) and 3-crotonoyl-1,3-oxazolidin-2-one (47 mg, 0.3 mmol). The ice-cooling bath was removed and the mixture was reacted at room temperature for 20 hours. A saturated aqueous solution of ammonium chloride was added to quench the reaction, and the reaction mixture was extracted with ethyl acetate. The organic layer was concentrated and purified by a silica gel column chromatography (hexane:ethyl acetate=4:1) to give the objective 3-[3-(4-methoxyphenylamino)butyryl]-1,3-oxazolidin-2-one (66.5 mg, 96% yield). The enantiomeric excess was determined by a liquid chromatography with an optical isomer separating column (column: AD-H) to be 94% e.e. was removed the mixture was reacted at room temperature for 20 hours to quench the reaction the reaction mixture was extracted with ethyl acetate The organic layer was concentrated purified by a silica gel column chromatography (hexane:ethyl acetate=4:1)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3-crotonoyl-1,3-oxazolidin-2-one (155 mg, 1.0 mmol) in ethyl acetate (3 ml) in a stream of nitrogen was added Pd((R)-binap)(H2O)2(OTf)2 (26.6 mg, 0.025 mmol), and the resulting mixture was cooled to 0° C. Aniline (0.11 ml, 1.2 mmol) was added to the mixture, and to the solution was added slowly methanesulfonic acid (0.078 ml, 1.2 mmol). Then, the cooling ice-bath was removed and the reaction mixture was reacted at room temperature for 18 hours with stirring. After completion of the reaction, the solvent was evaporated off, and the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective compound 3-(3-phenylaminobutyryl)-oxazolidin-2-one (37 mg, 15% yield). Enantiomeric excess ratio of this product was determined by a liquid chromatography using a column for separation of optical isomers (column: AD-H) to be 82% e.e. Then, the cooling ice-bath was removed the reaction mixture was reacted at room temperature for 18 hours After completion of the reaction the solvent was evaporated off the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3-crotonoyl-1,3-oxazolidin-2-one (155 mg, 1.0 mmol) in toluene (3 ml) in a stream of nitrogen was added Pd((R)-binap)(H2O)2(OTf)2 (26.6 mg, 0.025 mmol), and the resulting mixture was cooled to 0° C. Aniline (0.11 ml, 1.2 mmol) was added to the mixture, and to the solution was added slowly methanesulfonic acid (0.039 ml, 0.6 mmol). Then, the cooling ice-bath was removed and the reaction mixture was reacted at room temperature for 15 hours with stirring. After completion of the reaction, the solvent was evaporated off, and the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective compound 3-(3-phenylaminobutyryl)-oxazolidin-2-one (58 mg, 23% yield). Enantiomeric excess ratio of this product was determined by a liquid chromatography using a column for separation of optical isomers (column: AD-H) to be 78% e.e. Then, the cooling ice-bath was removed the reaction mixture was reacted at room temperature for 15 hours After completion of the reaction the solvent was evaporated off the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3-crotonoyl-1,3-oxazolidin-2-one (155 mg, 1.0 mmol) in toluene (3 ml) in a stream of nitrogen was added Pd((R)-binap)(H2O)2(OTf)2 (26.6 mg, 0.025 mmol), and the resulting mixture was cooled to 0° C. Aniline (0.11 ml, 1.2 mmol) was added to the mixture, and to the solution was added slowly methanesulfonic acid (0.039 ml, 0.6 mmol). Then, the cooling ice-bath was removed and the reaction mixture was reacted at room temperature for 15 hours with stirring. After completion of the reaction, the solvent was evaporated off, and the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective compound 3-(3-phenylaminobutyryl)-oxazolidin-2-one (58 mg, 23% yield). Enantiomeric excess ratio of this product was determined by a liquid chromatography using a column for separation of optical isomers (column: AD-H) to be 78% e.e. Then, the cooling ice-bath was removed the reaction mixture was reacted at room temperature for 15 hours After completion of the reaction the solvent was evaporated off the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-trifluoromethylaniline (193 mg, 1.2 mmol) and 3-crotonoyl-1,3-oxazolidin-2-one (155 mg, 1.0 mmol) in toluene (3 ml) in a stream of nitrogen was added Pd((R)-segphos)(H2O)2(OTf)2 (26.3 mg, 0.025 mmol) and the resulting mixture was stirred at room temperature for 14 hours. After completion of the reaction, a saturated aqueous solution of ammonium chloride (10 ml) was added to the reaction mixture and the resulting mixture was extracted with ethyl acetate (10 ml). The organic layer was dried over anhydrous magnesium sulfate. The solvent was then evaporated off and the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective compound 3-(4-trifluoromethylanilino)butyryl-1,3-oxazolidin-2-one (238 mg, 75% yield). Enantiomeric excess ratio of this product was determined by a liquid chromatography using a column for separation of optical isomers (column: AD-H) to be 84% e.e. After completion of the reaction the resulting mixture was extracted with ethyl acetate (10 ml) The organic layer was dried over anhydrous magnesium sulfate The solvent was then evaporated off the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-trifluoromethylaniline (193 mg, 1.2 mmol) and 3-crotonoyl-1,3-oxazolidin-2-one (155 mg, 1.0 mmol) in toluene (3 ml) in a stream of nitrogen was added Pd((R)-segphos)(H2O)2(OTf)2 (26.3 mg, 0.025 mmol) and the resulting mixture was stirred at room temperature for 14 hours. After completion of the reaction, a saturated aqueous solution of ammonium chloride (10 ml) was added to the reaction mixture and the resulting mixture was extracted with ethyl acetate (10 ml). The organic layer was dried over anhydrous magnesium sulfate. The solvent was then evaporated off and the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1) to give the objective compound 3-(4-trifluoromethylanilino)butyryl-1,3-oxazolidin-2-one (238 mg, 75% yield). Enantiomeric excess ratio of this product was determined by a liquid chromatography using a column for separation of optical isomers (column: AD-H) to be 84% e.e. After completion of the reaction the resulting mixture was extracted with ethyl acetate (10 ml) The organic layer was dried over anhydrous magnesium sulfate The solvent was then evaporated off the crude product obtained was purified by a silica gel column chromatography (hexane:ethyl acetate=1:1)