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Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation.


ABSTRACT: Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH]+ stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di- and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3 underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy- and siloxy-substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.

SUBMITTER: Schuhknecht D 

PROVIDER: S-EPMC6972613 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation.

Schuhknecht Danny D   Spaniol Thomas P TP   Maron Laurent L   Okuda Jun J  

Angewandte Chemie (International ed. in English) 20191119 1


Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH]<sup>+</sup> stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give  ...[more]

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