所属 崇城大学 薬学部 薬学科 崇城大学大学院 薬学研究科 薬学専攻 職種 教授
|標題||Lewis Base-Catalyzed Enantioselective Conjugate Reduction of β,β-Disubstituted α,β-Unsaturated Ketones with Trichlorosilane: E/Z-Isomerization, Regioselectivity, and Synthetic Applications.
[Highlighted in Organic Chemistry Portal; Featured in Org. Chem. Highlights: Alkylated Stereogenic Centers]
|掲載誌名||The Journal of Organic Chemistry|
|著者・共著者||Sugiura Masaharu, Ashikari Yasuhiko, Takahashi Yuka, Yamaguchi Koki, Kotani Shunsuke, Nakajima Makoto|
|概要||The chiral bisphosphine dioxide-catalyzed asymmetric conjugate reduction of acyclic β,β-disubstituted α,β-unsaturated ketones with trichlorosilane affords saturated ketones having a stereogenic carbon center at the carbonyl β-position with high enantioselectivities. Because the E/Z-isomerizations of enone substrates occur concomitantly, reduction products with the same absolute configurations are obtained from either (E)- or (Z)-enones. Conjugate reduction is accelerated in the presence of an electron-rich aryl group at the β-position of the enone owing to its carbocation-stabilizing ability. Computational studies were also conducted in order to elucidate the origin of the observed enantioselectivity. The regio- and enantioselective reductions of dienones were realized and applied to the syntheses of ar-turmerone, turmeronol A, mutisianthol, and jungianol, which are optically active sesquiterpenes.|