反应详情

To a toluene solution (22 ml) of (3S)-3-(tert-butyldimethylsiloxy)-5-phenyl-1-pentyne (1.96 g) was added n-butyl lithium (2.5 M, hexane solution, 2.64 ml) at 0° C., followed by stirring at room temperature for 30 minutes. To the solution was added diethylaluminum chloride (0.95 N, hexane solution, 8.10 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, 22.0 ml) at room temperature, followed by stirring for 15 minutes. The reaction solution was poured into a mixture of hexane (53 ml), a saturated aqueous ammonium chloride solution (53 ml) and an aqueous hydrochloric acid solution (3 N, 15.4 ml) with stirring, and the organic layer was separated and washed with a saturated aqueous sodium bicarbonate solution (20 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:ethyl acetate=49:1) to give (3R,4R)-2-methylene-3-[(3S)-3-tert-butyldimethylsiloxy-5-phenylpent-1-ynyl]-4-(tert-butyldimethylsiloxy)cyclopentan-1-one (1.65 g).

1. stirringby stirring at room temperature for 30 minutes
2. stirringby stirring for 15 minutes
3. customthe organic layer was separated
4. washwashed with a saturated aqueous sodium bicarbonate solution (20 ml)
5. dry with materialThe resulting organic layer was dried over anhydrous magnesium sulfate
6. filtrationfiltered
7. concentrationconcentrated
8. customthe resulting residue was purified by a silica gel column chromatography (developing solvent; hexane:ethyl acetate=49:1)