反应详情

In toluene (80 ml) was dissolved (3S)-3-(tert-butyldimethylsiloxy)-3-cyclohexylprop-1-yne (6.58 g), and n-butyl lithium (3.0 M, hexane solution, 8.0 ml) was added at 0° C., followed by stirring at the same temperature for 30 minutes. To the solution was added diethylaluminum chloride (0.95 M, hexane solution, 29.0 ml) at 0° C., followed by stirring at room temperature for 30 minutes. To the solution was added (4R)-2-(N,N-diethylamino)methyl-4-(tert-butyldimethylsiloxy)cyclopent-2-en-1-one (0.25 M, toluene solution, 80.0 ml) at room temperature, followed by stirring for 15 minutes. The reaction solution, while stirring, was added to a mixture of hexane (190 ml), a saturated aqueous ammonium chloride solution (190 ml) and an aqueous hydrochloric acid solution (3 M, 56 ml), and the organic layer was separated and washed with a saturated aqueous sodium bicarbonate solution (50 ml). The resulting organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and the resulting residue was purified by a silica gel column chromatography (developing solvent; hexane:ether=10:1) to give (3R,4R)-2-methylene-3-[(3S)-3-(tert-butyldimethylsiloxy)-3-cyclohexylprop-1-ynyl]-4-(tert-butyldimethylsiloxy)cyclopentan-1-one (7.92 g).

1. additionwas added at 0° C.
2. stirringby stirring at room temperature for 30 minutes
3. stirringby stirring for 15 minutes
4. stirringThe reaction solution, while stirring
5. customa saturated aqueous ammonium chloride solution (190 ml) and an aqueous hydrochloric acid solution (3 M, 56 ml), and the organic layer was separated
6. washwashed with a saturated aqueous sodium bicarbonate solution (50 ml)
7. dry with materialThe resulting organic layer was dried over anhydrous magnesium sulfate
8. filtrationfiltered
9. concentrationconcentrated
10. customthe resulting residue was purified by a silica gel column chromatography (developing solvent; hexane:ether=10:1)