Zirconocene-Catalyzed Silylation of Alkenes with Chlorosilanes

Terao, Jun; Torii, K.; Saito, Koyu; Kambe, Nobuaki; Baba, Akio; Sonoda, Noboru

doi:10.1002/(sici)1521-3773(19981016)37:19<2653::aid-anie2653>3.0.co;2-3

Cited by 64 publications

(16 citation statements)

References 7 publications

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“…In more recent years, the direct silylation of alkenes mediated by transition metal catalysts,11 e.g., iron,12 cobalt,13 palladium,14 rhodium,15 ruthenium,16 iridium,17 and rhenium18 complexes, was introduced. Additionally, Kambe et al reported the zirconocene catalyzed silylation of alkenes using chlorosilanes19 while Yorimitsu and Oshima developed an elegant silylation of terminal alkenes via Ni-catalyzed exchange with silacyclobutanes 20. However, there are some important limitations associated with the stoichiometric and catalytic reactions.…”

Section: Introductionmentioning

confidence: 99%

Iridium-Catalyzed (Z)-Trialkylsilylation of Terminal Olefins

Falck

2010

J. Org. Chem.

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A complex of commercial [Ir(OMe)(cod)]2 and 4,4-di-tert-butyl-2,2-bipyridine (dtbpy) catalyzes the Z-selective, dehydrative silylation of terminal alkenes, but not 1,2-disubstituted alkenes, with triethylsilane or benzyldimethylsilane in THF at 40 °C. Yields and Z-stereoselectivity were significantly improved by 2-norbornene, in contrast with other sacrificial alkenes. The reaction is compatible with many functional groups including epoxides, ketones, amides, alcohols, esters, halides, ketals and silanes. a,b-Unsaturated esters were unreactive. The reaction probably proceeds through a Heck-type mechanism.

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Section: Introductionmentioning

confidence: 99%

Iridium-Catalyzed (Z)-Trialkylsilylation of Terminal Olefins

Falck

2010

J. Org. Chem.

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“…We reported that alkenes underwent silylation by reaction with chlorosilanes employing the Cp 2 ZrCl 2 /n-BuMgCl system to give alkenyl and/or allylsilanes [17]. This reaction proceeds via zirconocene-olefin ate complexes with the olefinic carbon acting as a nucleophilic center toward chlorosilanes.…”

Section: Zr-catalyzed Hydroalkylation Of Stylenes Using Alkyl Fluoridesmentioning

confidence: 99%

“…For example, octyl fluoride (2 mmol) reacted with styrene (3 mmol) in the presence of a catalytic amount of zirconocene dichloride (0.05 molar amount) under THF reflux conditions to give 2-decylbenzene (17) in 70 % yield (Scheme 8). Interestingly, reactions using alkyl chloride (11 %) and bromide (52 %) were less efficient.…”

Section: Zr-catalyzed Hydroalkylation Of Stylenes Using Alkyl Fluoridesmentioning

confidence: 99%

Carbon-carbon bond-forming reactions using alkyl fluorides

Terao

Todo

Watabe

et al. 2008

Pure and Applied Chemistry

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This account summarizes our recent results on C-C bond formation reactions using alkyl fluorides mostly focusing on the transition-metal-catalyzed reactions. These reactions proceed efficiently under mild conditions by the combined use of Grignard reagents and transition-metal catalysts, such as Ni, Cu, and Zr. It is proposed that ate complex intermediates formed by the reaction of these transition metals with Grignard reagents play important roles as the active catalytic species. Organoaluminun reagents react directly with alkyl fluorides in nonpolar solvents at room temperature to form C-C bonds. These studies demonstrate the practical usefulness of alkyl fluorides in C-C bond formation reactions and provide a promising method for the construction of carbon frameworks employing alkyl fluorides. The scope and limitations, as well as reaction pathways, are discussed.

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“…In 1998, we disclosed the first instance of a silylation reaction of alkenes with chlorosilanes, which had been achieved with the aid of a zirconocene catalyst 14. This reaction is promoted by Grignard reagents to give alkenyl‐ and/or allylsilanes as products (Eq.…”

Section: Zr‐catalyzed Silylation Of Alkenes Using Chlorosilanesmentioning

confidence: 99%

“…This unique reactivity may arise from strong back donation from zirconium to the alkenes; this effect would be enhanced by formation of ate complexes 7 . It is proposed that the rate‐determining step is the ligand exchange process to regenerate the olefin complex 6 in the case of styrene and the β‐hydrogen elimination process from 8 in the case of allylbenzene 14b…”

Section: Zr‐catalyzed Silylation Of Alkenes Using Chlorosilanesmentioning

confidence: 99%

Transition metal catalyzed carbon‐silicon bond forming reactions using chlorosilanes promoted by Grignard reagents

Terao

Kambe

2007

The Chemical Record

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New catalytic C--Si bond-forming reactions using chlorosilanes are described. These reactions proceed efficiently under mild conditions by the combined use of Grignard reagents and transition metal catalysts, such as Ti, Zr, Ni, and Pd. It is proposed that ate complex intermediates formed by the reaction of transition metals with Grignard reagents play important roles as the active catalytic species. The present study demonstrates the practical use of chlorosilanes in transition metal catalyzed silylation reactions providing convenient methods for allyl- or vinylsilane synthesis. The reaction pathways of these transformations as well as the scope and limitations are discussed.

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Zirconocene-Catalyzed Silylation of Alkenes with Chlorosilanes

Cited by 64 publications

References 7 publications

Iridium-Catalyzed (Z)-Trialkylsilylation of Terminal Olefins

Iridium-Catalyzed (Z)-Trialkylsilylation of Terminal Olefins

Carbon-carbon bond-forming reactions using alkyl fluorides

Transition metal catalyzed carbon‐silicon bond forming reactions using chlorosilanes promoted by Grignard reagents

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