title: Stereoselective construction of 1,3-disilylcyclopentane derivatives by scandium-catalyzed [3+2] cycloaddition of allylsilanes to β-silylenones.
abstract: The Sc(OTf)3-catalyzed [3+2] cycloaddition of allylsilanes to β-silyl-α,β-unsaturated ketones (β-silylenones) has been developed to form five-membered syn-1,3-disilylketones diastereoselectively through the rearrangement of the silicon substituents on the allylsilane. Stabilization of the carbocation intermediates by a double silicon effect plays a key role in directing the course of the reaction to favor the [3+2] cycloaddition pathway over simple allylation.
authors: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan) http://www.ehcc.kyoto-u.ac.jp/eh31/home/index-j.html. kokamoto@scl.kyoto-u.ac.jp.
authors: Kazuhiro
authors: K
authors: Okamoto
authors: Eisuke
authors: E
authors: Tamura
authors: Kouichi
authors: K
authors: Ohe
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003517:Cyclopentanes / Q000138:chemical synthesis / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012538:Scandium / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: C000598010:1,3-disilylcyclopentane; D000475:Alkenes; D003517:Cyclopentanes; D007659:Ketones; D009942:Organometallic Compounds; D012821:Silanes; C511847:allylsilane; D012538:Scandium
keywords: cycloaddition; diastereoselectivity; homogeneous catalysis; scandium; silicon