(Methoxymethylene)triphenylphosphorane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of (methoxymethylene)triphenylphosphorane (6.74 g, 21.99 mmol) in tetrahydrofuran (30 mL) was added drop-wise a solution of potassium tert-butoxide (3.08 g, 27.5 mmol) in THF at −30° C. under argon, and the mixture was stirred for 30 min. Then a solution of (R)-3′,4′-dihydro-2′H-spiro[[1,3]dioxolane-2,1′-naphthalene]-3′-carbaldehyde (4.0 g, 18.33 mmol) in THF was added drop-wise and reaction was stirred for 1 h at −30° C. Reaction was monitored by TLC. Reaction mixture quenched with water at −30° C. and allowed to RT, diluted with water (25 mL) and extracted with ethyl acetate (2×50 mL), dried over Na2SO4, filtered and concentrated to give crude product (8 g). The crude compound was purified with silica gel flash column chromatography (Biotage) to give (R)-3′-(2-methoxyvinyl)-3′,4′-dihydro-2′H-spiro[[1,3]dioxolane-2,1′-naphthalene] (3.5 g, 14.21 mmol, 78% yield) as colourless liquid; m/z 246.6. drop-wise and reaction was stirred for 1 h at −30° C Reaction Reaction mixture quenched with water at −30° C. allowed to RT diluted with water (25 mL) extracted with ethyl acetate (2×50 mL) dried over Na2SO4 filtered concentrated to give crude product (8 g) The crude compound was purified with silica gel flash column chromatography (Biotage)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of (methoxymethylene)triphenylphosphorane (6.74 g, 21.99 mmol) in tetrahydrofuran (30 mL) was added drop-wise a solution of potassium tert-butoxide (3.08 g, 27.5 mmol) in THF at −30° C. under argon, and the mixture was stirred for 30 min. Then a solution of (R)-3′,4′-dihydro-2′H-spiro[[1,3]dioxolane-2,1′-naphthalene]-3′-carbaldehyde (4.0 g, 18.33 mmol) in THF was added drop-wise and reaction was stirred for 1 h at −30° C. Reaction was monitored by TLC. Reaction mixture quenched with water at −30° C. and allowed to RT, diluted with water (25 mL) and extracted with ethyl acetate (2×50 mL), dried over Na2SO4, filtered and concentrated to give crude product (8 g). The crude compound was purified with silica gel flash column chromatography (Biotage) to give (R)-3′-(2-methoxyvinyl)-3′,4′-dihydro-2′H-spiro[[1,3]dioxolane-2,1′-naphthalene] (3.5 g, 14.21 mmol, 78% yield) as colourless liquid; m/z 246.6. drop-wise and reaction was stirred for 1 h at −30° C Reaction Reaction mixture quenched with water at −30° C. allowed to RT diluted with water (25 mL) extracted with ethyl acetate (2×50 mL) dried over Na2SO4 filtered concentrated to give crude product (8 g) The crude compound was purified with silica gel flash column chromatography (Biotage)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of methoxymethylenetriphenylphosphorane is prepared by addition of lithium diisopropyl amide (10.6 g, 0.1 mole) in dry tetrahydrofuran (100 ml) to a slurry of methoxy methyl triphenyl phosphonium chloride (34.3 g, 0.1 mole) in dry toluene (400 ml) under nitrogen at 0° C. The resulting red Wittig reagent is stirred at 0° C. for 30 minutes prior to use. To this solution is added endo-5-t-butyldimethylsilyloxy-exo-3a, 4,7,7a-tetrahydro-4,7-epoxyisobenzofuran-2-ol (14.3 g, 0.05 mole) via a solids addition funnel and the resulting mixture is stirred at 25° C. for 2 hours. The mixture is acidified to pH 5 with 10hydrochloric acid and extracted with ether (three 200 ml portions). The solvents are removed under vacuum and the residue is dissolved in ether and this solution chilled yielding crystalline triphenylphosphine oxide. The filtrate is concentrated yielding the title compound which is purified by column chromatography on silica gel. via a solids addition funnel extracted with ether (three 200 ml portions) The solvents are removed under vacuum the residue is dissolved in ether this solution chilled

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of (methoxymethylene)triphenylphosphorane (6.74 g, 21.99 mmol) in tetrahydrofuran (30 mL) was added drop-wise a solution of potassium tert-butoxide (3.08 g, 27.5 mmol) in THF at −30° C. under argon, and the mixture was stirred for 30 min. Then a solution of (R)-3′,4′-dihydro-2′H-spiro[[1,3]dioxolane-2,1′-naphthalene]-3′-carbaldehyde (4.0 g, 18.33 mmol) in THF was added drop-wise and reaction was stirred for 1 h at −30° C. Reaction was monitored by TLC. Reaction mixture quenched with water at −30° C. and allowed to RT, diluted with water (25 mL) and extracted with ethyl acetate (2×50 mL), dried over Na2SO4, filtered and concentrated to give crude product (8 g). The crude compound was purified with silica gel flash column chromatography (Biotage) to give (R)-3′-(2-methoxyvinyl)-3′,4′-dihydro-2′H-spiro[[1,3]dioxolane-2,1′-naphthalene] (3.5 g, 14.21 mmol, 78% yield) as colourless liquid; m/z 246.6. drop-wise and reaction was stirred for 1 h at −30° C Reaction Reaction mixture quenched with water at −30° C. allowed to RT diluted with water (25 mL) extracted with ethyl acetate (2×50 mL) dried over Na2SO4 filtered concentrated to give crude product (8 g) The crude compound was purified with silica gel flash column chromatography (Biotage)