スギウラ マサハル   Sugiura Masaharu
  杉浦 正晴
   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
言語種別 英語
発行・発表の年月 2019/08
形態種別 原著論文
査読 査読有り
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]
執筆形態 共著
掲載誌名 The Journal of Organic Chemistry
掲載区分国外
巻・号・頁 84(18),pp.11458-11473
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.
DOI 10.1021/acs.joc.9b01298
ISSN 1520-6904
PMID 31449412
PermalinkURL https://www.organic-chemistry.org/Highlights/2020/20July.shtm