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Catalytic Difunctionalization of Unactivated Alkenes with Unreactive Hexamethyldisilane through Regeneration of Silylium Ions.

ABSTRACT: A metal-free, intermolecular syn-addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium-ion-like intermediate, corresponding to the (re)generation of the silylium-ion catalyst. The key feature of the reaction sequence is the cleavage of the Si-Si bond in a 1,3-silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X-ray diffraction, and the computed reaction mechanism is fully consistent with the experimental findings.

SUBMITTER: Wu Q

PROVIDER: S-EPMC6900109 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Catalytic Difunctionalization of Unactivated Alkenes with Unreactive Hexamethyldisilane through Regeneration of Silylium Ions.

Wu Qian Q Roy Avijit A Irran Elisabeth E Qu Zheng-Wang ZW Grimme Stefan S Klare Hendrik F T HFT Oestreich Martin M

Angewandte Chemie (International ed. in English) 20191023 48

A metal-free, intermolecular syn-addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium-ion-like intermediate, corresponding to the (re)generation of the silylium-ion catalyst. The key feature of the reaction sequence is the cleavage of the Si-Si bond in a 1,3-silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X-ra ...[more]

PMID: 31566863

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