反应详情

温度

0 °C

A solution of 2-(1,3-dioxolane-2-yl)-3-[(thiophen-3-yl)hydroxymethyl]-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (1.31 g, 3.86 mmol) [prepared from 3-bromo-2-(1,3-dioxolane-2-yl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene and 3-thiophenecarboxaldehyde as previously described for the preparation of 2-(1,3-dioxolane-2-yl)-3-[(thiophene-2-yl)hydroxymethyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene] in 13 ml of anhydrous dichloromethane was cooled to 0° C. and Des-Martin periodinane (1.80 g, 4.25 mmol) was added over 3 minutes. The reaction was warmed to rt and stirred for 4 hours. The cloudy solution was diluted with 200 ml of dichloromethane and washed with sodium bicarbonate solution. The organic layer was washed with brine, dried over magnesium sulfate and concentrated in vacuo. This residue was then dissolved in 10 ml of tetrahydrofuran and stirred vigorously while adding 10 ml of an aqueous 1N HCl solution. Mixture was stirred for two hours and partitioned between ethyl acetate and water. The resulting organic layer was washed with brine, dried over magnesium sulfate and dried in vacuo. Chromatographic separation was achieved using a silica gel column eluting with a gradient starting with 2% ethyl acetate/hexanes to 8% ethyl acetate/hexanes to give 2-formyl-[3-((thiophen-3-yl)oxomethyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (386 mg).

1. additionDes-Martin periodinane (1.80 g, 4.25 mmol) was added over 3 minutes
2. temperatureThe reaction was warmed to rt
3. washwashed with sodium bicarbonate solution
4. washThe organic layer was washed with brine
5. dry with materialdried over magnesium sulfate
6. concentrationconcentrated in vacuo
7. dissolutionThis residue was then dissolved in 10 ml of tetrahydrofuran
8. stirringstirred vigorously
9. additionwhile adding 10 ml of an aqueous 1N HCl solution
10. stirringMixture was stirred for two hours
11. custompartitioned between ethyl acetate and water
12. washThe resulting organic layer was washed with brine
13. dry with materialdried over magnesium sulfate
14. customdried in vacuo
15. customChromatographic separation
16. washeluting with