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[摘要]:We report a novel asym. addn. of vinyl group to ketones using vinylaluminum reagents catalyzed by in situ prepd. Ti(OiPr)4 complexes of (S)-BINOL to afford diversified tertiary allylic alcs. Varieties of arom. ketones bearing either an electron-donating or an electron-withdrawing substituent on the arom. ring were examd. to afford products in excellent enantioselectivities of up to 98% ee with high yields. A 10-fold scale-up reaction afforded the product in a similar yield with a comparable enantioselectivity. More importantly, addns. of a variety of vinyl reagents including functionalized vinyls were demonstrated, affording tertiary allylic alcs. with good to excellent enantioselectivities of up to 96% ee. |
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