methyl (E)-4-phenylbut-3-enoate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In an analogous manner to that described in Example 5 (b), by reducing methyl (E)-4-phenyl-but-3-enoate by means of lithium aluminium hydride in tetrahydrofuran there was obtained (E)-4-phenyl-but-3-en-1-ol, which was converted into (E)-4-phenyl-but-3-enyl methanesulphonate in analogy to the procedure described in J.Chem.Soc. Perk.Trans. 1 (1988), (6), 1517-1519 for the preparation of the (Z) isomer.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In an analogous manner to that described in Example 5 (b), by reducing methyl (E)-4-phenyl-but-3-enoate by means of lithium aluminium hydride in tetrahydrofuran there was obtained (E)-4-phenyl-but-3-en-1-ol, which was converted into (E)-4-phenyl-but-3-enyl methanesulphonate in analogy to the procedure described in J.Chem.Soc. Perk.Trans. 1 (1988), (6), 1517-1519 for the preparation of the (Z) isomer.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3.24 mg (20 mmol) of (E)-styrylacetic acid in 20 ml of methanol, 2 ml of trimethyl orthoformate and 192 mg (2 mmol) of methanesulphonic acid was stirred at 50° C. under argon for one hour. For the working-up, the mixture was neutralized with 2 mmol of sodium methylate and subsequently the solvent mixture was distilled off under reduced pressure. There was obtained methyl (E)-4-phenyl-but-3-enoate as a colourless liquid in quantitative yield; MS: 176 (M)+. subsequently the solvent mixture was distilled off under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl (E)-2-diazo-4-phenyl-3-butenoate (9) was prepared according to the procedure described in Davies, et al., J. Org. Chem., 56:3817 (1997) (“Davies II”), which is hereby incorporated by reference). The scheme is set forth in FIG. 7B. Briefly, to a stirred solution of methyl trans-4-phenylbut-3-enoate (1.0 g, 5.68 mmol) and p-ABSA (1.64 g, 6.82 mmol) in CH3CN (150 mL) cooled to 0° C., was added DBU (0.95 g, 6.25 mmol) in one portion. The reaction mixture was allowed to warm to room temperature over 7 h then quenched with saturated ammonium chloride (NH4Cl). The aqueous layer was extracted with diethyl ether, and the combined organic layers were washed with brine and dried (Na2SO4). The solvent was removed under reduced pressure, and the residue was triturated with a solution of pentane/diethyl:ether (1:1). The solid was filtered off, and the solvent was removed under reduced pressure. The residue was purified by flash chromatography (SiO2, pentane/diethyl:ether (15:1)) to give methyl (E)-2-diazo-4-phenyl-3-butenoate (9) (0.92 g, 80% yield) as an orange oil, which was stored neat at −10° C. until ready for use. The spectroscopic data are consistent with previously reported data ((Davies II, which is hereby incorporated by reference). Methyl (E)-2-diazo-4-phenyl-3-butenoate (9) was prepared then quenched with saturated ammonium chloride (NH4Cl) The aqueous layer was extracted with diethyl ether the combined organic layers were washed with brine dried (Na2SO4) The solvent was removed under reduced pressure the residue was triturated with a solution of pentane/diethyl The solid was filtered off the solvent was removed under reduced pressure The residue was purified by flash chromatography (SiO2, pentane/diethyl:ether (15:1))

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (E)-methyl 4-phenylbut-3-enoate (S32) and p-ABSA (see reference above for preparation of p-ABSA) in CH3CN cooled to 0° C., was added DBU. The reaction mixture was allowed to warm to room temperature over 7 h then quenched with saturated ammonium chloride (NH4Cl). The aqueous layer was extracted with diethyl ether three times and the combined organic layers were washed with brine and dried over Na2SO4. The solvent was removed under reduced pressure and the residue was triturated with a solution of pentane:diethyl ether (1:1). The solid was filtered off and the solvent was removed under reduced pressure. The residue was purified by flash chromatography (SiO2, pentane:diethyl ether (15:1)) to give the title compound (S33) in 68% yield as a dark red solid, which was stored neat at −10° C. until ready for use. then quenched with saturated ammonium chloride (NH4Cl) The aqueous layer was extracted with diethyl ether three times the combined organic layers were washed with brine dried over Na2SO4 The solvent was removed under reduced pressure the residue was triturated with a solution of pentane:diethyl ether (1:1) The solid was filtered off the solvent was removed under reduced pressure The residue was purified by flash chromatography (SiO2, pentane:diethyl ether (15:1))

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Phenylbut-3-enoic acid was dissolved in acetone and added to Cs2CO3, then MeI was added. The suspension was refluxed overnight. Et2O and brine were added and the phases separated. Aqueous layer was washed three times with Et2O. Combined organic layers were dried over MgSO4 and the solvent was evaporated in vacuum. (E)-methyl 4-phenylbut-3-enoate (S32) was obtained as a yellow oil (quantitative). Rf (hexane/EtOAc 8:1)=0.28. The suspension was refluxed overnight the phases separated Aqueous layer was washed three times with Et2O Combined organic layers were dried over MgSO4 the solvent was evaporated in vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Phenylbut-3-enoic acid was dissolved in acetone and added to Cs2CO3, then MeI was added. The suspension was refluxed overnight. Et2O and brine were added and the phases separated. Aqueous layer was washed three times with Et2O. Combined organic layers were dried over MgSO4 and the solvent was evaporated in vacuum. (E)-methyl 4-phenylbut-3-enoate (S32) was obtained as a yellow oil (quantitative). Rf (hexane/EtOAc 8:1)=0.28. The suspension was refluxed overnight the phases separated Aqueous layer was washed three times with Et2O Combined organic layers were dried over MgSO4 the solvent was evaporated in vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl (E)-2-diazo-4-phenyl-3-butenoate (9) was prepared according to the procedure described in Davies, et al., J. Org. Chem., 56:3817 (1997) (“Davies II”), which is hereby incorporated by reference). The scheme is set forth in FIG. 7B. Briefly, to a stirred solution of methyl trans-4-phenylbut-3-enoate (1.0 g, 5.68 mmol) and p-ABSA (1.64 g, 6.82 mmol) in CH3CN (150 mL) cooled to 0° C., was added DBU (0.95 g, 6.25 mmol) in one portion. The reaction mixture was allowed to warm to room temperature over 7 h then quenched with saturated ammonium chloride (NH4Cl). The aqueous layer was extracted with diethyl ether, and the combined organic layers were washed with brine and dried (Na2SO4). The solvent was removed under reduced pressure, and the residue was triturated with a solution of pentane/diethyl:ether (1:1). The solid was filtered off, and the solvent was removed under reduced pressure. The residue was purified by flash chromatography (SiO2, pentane/diethyl:ether (15:1)) to give methyl (E)-2-diazo-4-phenyl-3-butenoate (9) (0.92 g, 80% yield) as an orange oil, which was stored neat at −10° C. until ready for use. The spectroscopic data are consistent with previously reported data ((Davies II, which is hereby incorporated by reference). Methyl (E)-2-diazo-4-phenyl-3-butenoate (9) was prepared then quenched with saturated ammonium chloride (NH4Cl) The aqueous layer was extracted with diethyl ether the combined organic layers were washed with brine dried (Na2SO4) The solvent was removed under reduced pressure the residue was triturated with a solution of pentane/diethyl The solid was filtered off the solvent was removed under reduced pressure The residue was purified by flash chromatography (SiO2, pentane/diethyl:ether (15:1))

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In an analogous manner to that described in Example 5(b), by reducing methyl (E)-4-phenyl-but-3-enoate by means of lithium aluminium hydride in tetrahydrofuran there was obtained (E)-4-phenyl-but-3-en-1-ol, which was converted into (E)-4-phenyl-but-3-enyl methanesulphonate in analogy to the procedure described in J.Chem.Soc. Perk.Trans. 1 (1988), (6),1517-1519 for the preparation of the (Z) isomer.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3.24 mg (20 mmol) of (E)-styrylacetic acid in 20 ml of methanol,2 ml of trimethyl orthoformate and 192 mg (2 mmol) of methanesulphonic acid was stirred at 50° C. under argon for one hour. For the working-up, the mixture was neutralized with 2 mmol of sodium methylate and subsequently the solvent mixture was distilled off under reduced pressure. There was obtained methyl (E)-4-phenyl-but-3-enoate as a colourless liquid in quantitative yield; MS: 176 (M)+. subsequently the solvent mixture was distilled off under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In an analogous manner to that described in Example 5 (b), by reducing methyl (E)-4-phenyl-but-3-enoate by means of lithium aluminium hydride in tetrahydrofuran there was obtained (E)-4-phenyl-but-3-en-1-ol, which was converted into (E)-4-phenyl-but-3-enyl methanesulphonate in analogy to the procedure described in J.Chem.Soc. Perk.Trans. 1 (1988), (6), 1517-1519 for the preparation of the (Z) isomer.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3.24 mg (20 mmol) of (E)-styrylacetic acid in 20 ml of methanol, 2 ml of trimethyl orthoformate and 192 mg (2 mmol) of methanesulphonic acid was stirred at 50° C. under argon for one hour. For the working-up, the mixture was neutralized with 2 mmol of sodium methylate and subsequently the solvent mixture was distilled off under reduced pressure. There was obtained methyl (E)-4-phenyl-but-3-enoate as a colourless liquid in quantitative yield; MS: 176 (M)+. subsequently the solvent mixture was distilled off under reduced pressure