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.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Catalytic Difunctionalization of Unactivated Alkenes with Unreactive Hexamethyldisilane through Regeneration of Silylium Ions ; volume:58 ; number:48 ; year:2019 ; pages:17307-17311 ; extent:5
Angewandte Chemie / International edition. International edition ; 58, Heft 48 (2019), 17307-17311 (gesamt 5)
- Creator
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Wu, Qian
Roy, Avijit
Irran, Elisabeth
Qu, Zheng‐Wang
Grimme, Stefan
Klare, Hendrik F. T.
Oestreich, Martin
- DOI
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10.1002/anie.201911282
- URN
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urn:nbn:de:101:1-2022080608252103756856
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.2025, 7:27 AM CEST
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Associated
- Wu, Qian
- Roy, Avijit
- Irran, Elisabeth
- Qu, Zheng‐Wang
- Grimme, Stefan
- Klare, Hendrik F. T.
- Oestreich, Martin
Other Objects (12)
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Intermolecular Carbosilylation of α‐Olefins with C(sp3)−C(sp) Bond Formation Involving Silylium‐Ion Regeneration
Catalytic difunctionalization of unactivated alkenes with unreactive hexamethyldisilane through regeneration of silylium ions
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Katalytische Difunktionalisierung von nichtaktivierten Alkenen mit reaktionsträgem Hexamethyldisilan durch Neubildung von Silyliumionen
Intermolekulare Carbosilylierung von α‐Olefinen mit C (sp 3)−C (sp)‐Bindungsknüpfung unter Neubildung von Silyliumionen
Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene‐Based Chiral Hydride Source
Intermolecular Carbosilylation of α‐Olefins with C (sp 3)−C (sp) Bond Formation Involving Silylium‐Ion Regeneration
(-)-Spartein-vermittelte stereoselektive intramolekulare Carbolithiierung von in Allyl- oder Propargyl-Stellung funktionalisierten Mehrfachbindungssystemen
Origin of the Ligand Ring‐Size Effect on the Catalytic Activity of Cationic Calcium Hydride Dimers in the Hydrogenation of Unactivated 1‐Alkenes
Calcium Hydride Cation Dimer Catalyzed Hydrogenation of Unactivated 1‐Alkenes and H 2 Isotope Exchange: Competitive Ca−H−Ca Bridges and Terminal Ca−H Bonds
Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B (C 6 F 5) 3 ‐Initiated Grob Fragmentation
Intermolecular Carbosilylation of α‐Olefins with C(sp3)−C(sp) Bond Formation Involving Silylium‐Ion Regeneration
Catalytic difunctionalization of unactivated alkenes with unreactive hexamethyldisilane through regeneration of silylium ions
Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene‐Based Chiral Hydride Source
Unterscheidung der enantiotopen Seiten von strukturell unvoreingenommenen Carbeniumionen unter Verwendung einer cyclohexadienbasierten, chiralen Hydridquelle
Katalytische Difunktionalisierung von nichtaktivierten Alkenen mit reaktionsträgem Hexamethyldisilan durch Neubildung von Silyliumionen
Intermolekulare Carbosilylierung von α‐Olefinen mit C (sp 3)−C (sp)‐Bindungsknüpfung unter Neubildung von Silyliumionen
Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene‐Based Chiral Hydride Source
Intermolecular Carbosilylation of α‐Olefins with C (sp 3)−C (sp) Bond Formation Involving Silylium‐Ion Regeneration
(-)-Spartein-vermittelte stereoselektive intramolekulare Carbolithiierung von in Allyl- oder Propargyl-Stellung funktionalisierten Mehrfachbindungssystemen
Origin of the Ligand Ring‐Size Effect on the Catalytic Activity of Cationic Calcium Hydride Dimers in the Hydrogenation of Unactivated 1‐Alkenes
Calcium Hydride Cation Dimer Catalyzed Hydrogenation of Unactivated 1‐Alkenes and H 2 Isotope Exchange: Competitive Ca−H−Ca Bridges and Terminal Ca−H Bonds
Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B (C 6 F 5) 3 ‐Initiated Grob Fragmentation