methyl 9-oxononanoate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of methyl 9-oxononanate (5.26 g) in THF (60 ml) was dropwise added 0.95M vinyl magnesium bromide (31.1 ml) at −30° C. and then stirred for 30 minutes at −25° C. The reaction mixture was poured into saturated ammonium chloride aqueous solution and then extracted with diethyl ether. The organic layer was washed with saturated brine, dried over magnesium sulfate anhydride, and then evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1) to give methyl 9-hydroxy-10-undecenate (3.41 g, 56.3%). at −30° C. extracted with diethyl ether The organic layer was washed with saturated brine dried over magnesium sulfate anhydride evaporated under reduced pressure The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1)

Conditions: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of methyl 9-oxononanate (260.4 mg) in THF (4 ml) was dropwise added 0.95M vinyl magnesium bromide (1.62 ml) at —70° C. and then stirred for 1 hour at −60° C. The reaction mixture was poured into a saturated ammonium chloride aqueous solution and then extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate anhydride, and then evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1) to give methyl 9-hydroxy-10-undecenate (144 mg, 47.4%). at —70° C. extracted with ethyl acetate The organic layer was washed with saturated brine dried over magnesium sulfate anhydride evaporated under reduced pressure The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1)

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

Procedure: To a solution of the crude product (4.71 g) in THF (50 ml) was dropwise added a solution of lithium aluminum hydrate tri-tert-butoxide (6.1 g) in THF (50 ml) and then stirred for 1.5 hours at room temperature. The reaction mixture which volume was reduced to about 50 ml by partial evaporation of the solvent under reduced pressure, was poured into 1N hydrochloric acid (200 ml) and then extracted with ethyl acetate. The organic layer was washed with water and saturated brine successively, and then dried over magnesium sulfate anhydride. The solvent was evaporated under reduced pressure to give methyl 9-oxononanate (3.33 g 89.3%). The reaction mixture which volume was reduced to about 50 ml by partial evaporation of the solvent under reduced pressure was poured into 1N hydrochloric acid (200 ml) extracted with ethyl acetate The organic layer was washed with water and saturated brine successively dried over magnesium sulfate anhydride The solvent was evaporated under reduced pressure

Conditions: temp:-25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of methyl 9-oxononanate (5.26 g) in THF (60 ml) was dropwise added 0.95M vinyl magnesium bromide (31.1 ml) at −30° C. and then stirred for 30 minutes at −25° C. The reaction mixture was poured into saturated ammonium chloride aqueous solution and then extracted with diethyl ether. The organic layer was washed with saturated brine, dried over magnesium sulfate anhydride, and then evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1) to give methyl 9-hydroxy-10-undecenate (3.41 g, 56.3%). at −30° C. extracted with diethyl ether The organic layer was washed with saturated brine dried over magnesium sulfate anhydride evaporated under reduced pressure The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1)

Conditions: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of methyl 9-oxononanate (260.4 mg) in THF (4 ml) was dropwise added 0.95M vinyl magnesium bromide (1.62 ml) at —70° C. and then stirred for 1 hour at −60° C. The reaction mixture was poured into a saturated ammonium chloride aqueous solution and then extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate anhydride, and then evaporated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1) to give methyl 9-hydroxy-10-undecenate (144 mg, 47.4%). at —70° C. extracted with ethyl acetate The organic layer was washed with saturated brine dried over magnesium sulfate anhydride evaporated under reduced pressure The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=3:1)

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

Procedure: To a solution of the crude product (4.71 g) in THF (50 ml) was dropwise added a solution of lithium aluminum hydrate tri-tert-butoxide (6.1 g) in THF (50 ml) and then stirred for 1.5 hours at room temperature. The reaction mixture which volume was reduced to about 50 ml by partial evaporation of the solvent under reduced pressure, was poured into 1N hydrochloric acid (200 ml) and then extracted with ethyl acetate. The organic layer was washed with water and saturated brine successively, and then dried over magnesium sulfate anhydride. The solvent was evaporated under reduced pressure to give methyl 9-oxononanate (3.33 g 89.3%). The reaction mixture which volume was reduced to about 50 ml by partial evaporation of the solvent under reduced pressure was poured into 1N hydrochloric acid (200 ml) extracted with ethyl acetate The organic layer was washed with water and saturated brine successively dried over magnesium sulfate anhydride The solvent was evaporated under reduced pressure

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

Procedure: To a solution of the crude product (4.71 g) in THF (50 ml) was dropwise added a solution of lithium aluminum hydrate tri-tert-butoxide (6.1 g) in THF (50 ml) and then stirred for 1.5 hours at room temperature. The reaction mixture which volume was reduced to about 50 ml by partial evaporation of the solvent under reduced pressure, was poured into 1N hydrochloric acid (200 ml) and then extracted with ethyl acetate. The organic layer was washed with water and saturated brine successively, and then dried over magnesium sulfate anhydride. The solvent was evaporated under reduced pressure to give methyl 9-oxononanate (3.33 g 89.3%). The reaction mixture which volume was reduced to about 50 ml by partial evaporation of the solvent under reduced pressure was poured into 1N hydrochloric acid (200 ml) extracted with ethyl acetate The organic layer was washed with water and saturated brine successively dried over magnesium sulfate anhydride The solvent was evaporated under reduced pressure

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 18.2 g (43 mmol) of 4-chlorobenzyltriphenylphosphonium chloride in 200 mL of dry tetrahydrofuran at -78° C. is added dropwise, 30.7 mL (43 mmol) of a 1.4M solution of potassium hexamethyldisilazide in tetrahydrofuran. This is allowed to stir for 1 hour when 8.0 g (43 mmol) of 8-carbomethoxyoctanal is added dropwise. The solution is stirred at -78° C. for 2 hours, allowed to warm to room temperature, and stirred for 2 days. The reaction is worked up by adding water and extracting three times with diethyl ether. The ether extracts are combined, washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to give a yellow solid. Pad filtration through flash silica gel eluting with 10% ethyl acetate/hexane, gives a yellow oil after concentration in vacuo. Flash chromatography on a 60 mm×150 mm silica column eluting with 5% ethyl acetate/hexane gives 1.62 g (13%) of 10-(4-chlorophenyl)-dec-9-enoic acid methyl ester as a mixture of E and Z isomers. is added dropwise to warm to room temperature stirred for 2 days extracting three times with diethyl ether washed with brine dried over Na2SO4 filtered concentrated in vacuo to give a yellow solid Pad filtration through flash silica gel eluting with 10% ethyl acetate/hexane gives a yellow oil after concentration in vacuo Flash chromatography on a 60 mm×150 mm silica column eluting with 5% ethyl acetate/hexane

Conditions: temp:0.00; pressure:0.00; stir: