文章基本信息

标题：Catalytic Asymmetric trans-Selective Hydrosilylation of Bisalkynes to Access AIE and CPL-Active Silicon-Stereogenic Benzosiloles
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作者：Ren-He Tang ; Zheng Xu ; Yi-Xue Nie 等
期刊名称：iScience
印刷版ISSN：2589-0042
出版年度：2020
卷号：23
期号：7
页码：1-122
DOI：10.1016/j.isci.2020.101268
语种：English
出版社：Elsevier
摘要：SummaryChirality widely exists in a diverse array of biologically active molecules and life forms, and the catalytic constructions of chiral molecules have triggered a heightened interest in the fields of chemistry and materials and pharmaceutical sciences. However, the synthesis of silicon-stereogenic organosilicon compounds is generally recognized as a much more difficult task than that of carbon-stereogenic centers because of no abundant organosilicon-based chiral sources in nature. Herein, we reported a highly enantioselective rhodium-catalyzedtrans-selective hydrosilylation of silicon-tethered bisalkynes to access chiral benzosiloles bearing a silicon-stereogenic center. This protocol featured with chiral Ar-BINMOL-Phos bearing hydrogen-bond donors as a privileged P-ligand for catalytic asymmetric hydrosilylation that is operationally simple and has 100% atom-economy with good functional group tolerability as well as high enantioselectivity (up to >99:1er). Benefiting from thetrans-selective hydrosilylation with the aid of Rh/Ar-BINMOL-Phos-based asymmetric catalysis, the Si-stereogenic benzosiloles exhibited pronounced aggregation-induced emission (AIE) and circularly polarized luminescence (CPL) activity.Graphical AbstractDisplay OmittedHighlights•Precise and facile construction of silicon-stereogenic center by desymmetrization•Highly enantioselective Rh-catalyzed hydrosilylation controlled by MFMC P,O,O-ligand•Catalytic asymmetric synthesis of AIE- and CPL-active chiral Si-center benzosiloles•The proposed mechanism is supported by NMR and kinetic studiesChemistry; Organic Synthesis; Stereochemistry