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- W4313480440 abstract "Given the powerful potential of chiral-at-silicon chemistry, enantioselective synthesis of Si-stereogenic centers has attracted substantial research interest in recent years. However, the catalytic asymmetric synthesis of Si-stereogenic organosilicon compounds remains an appealing venture and is a challenging subject because of the difficulty in achieving high reactivity and stereoselectivity for silicon-center transformations. Herein, we disclose a highly enantioselective palladium-catalyzed hydrosilylation of 1,3-diynes with dihydrosilanes, which enables the facile preparation of Si-stereogenic enynes and an enyne-linked chiral polymer (polyenyne) in good yields and excellent ees (up to >99%) by desymmetrization. The unusual stereoselectivity in this reaction is achieved by precisely controlling the steric hindrance and electronic effect of the newly developed chiral ligands, resulting in a wide range of chiral silanes and a Si-containing polymer bearing a Si-stereogenic center which is otherwise difficult to access. The key to the high enantioselectivity relies on catalyst aggregation-induced non-covalent interaction, which exerts a remarkably positive influence on the Si-H bond activation and enhancement of enantioselectivity, in which the palladium/P-ligand complex was proved to be air-stable and moisture-insensitive in this reaction." @default.
- W4313480440 created "2023-01-06" @default.
- W4313480440 creator A5002588191 @default.
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- W4313480440 creator A5029888200 @default.
- W4313480440 creator A5054945722 @default.
- W4313480440 creator A5081268784 @default.
- W4313480440 date "2023-01-01" @default.
- W4313480440 modified "2023-10-18" @default.
- W4313480440 title "An unusual autocatalysis with an air-stable Pd complex to promote enantioselective synthesis of Si-stereogenic enynes" @default.
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- W4313480440 doi "https://doi.org/10.1039/d2sc06181c" @default.
- W4313480440 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/36756338" @default.
- W4313480440 hasPublicationYear "2023" @default.
- W4313480440 type Work @default.