Catalytic Asymmetric trans-Selective Hydrosilylation of Bisalkynes to Access AIE and CPL-Active Silicon-Stereogenic Benzosiloles
Ren-He Tang,
Zheng Xu,
Yi-Xue Nie,
Xu-Qiong Xiao,
Ke-Fang Yang,
Jia-Le Xie,
Bin Guo,
Guan-Wu Yin,
Xue-Min Yang,
Li-Wen Xu
Affiliations
Ren-He Tang
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Zheng Xu
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Yi-Xue Nie
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Xu-Qiong Xiao
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Ke-Fang Yang
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Jia-Le Xie
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Bin Guo
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Guan-Wu Yin
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Xue-Min Yang
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China
Li-Wen Xu
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, P. R. China; State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute (SRI), Lanzhou Institute of Chemical Physics (LICP), University of the Chinese Academy of Sciences (UCAS), Lanzhou 730000, P. R. China; Corresponding author
Summary: Chirality 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-catalyzed trans-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 >99:1 er). Benefiting from the trans-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.
