The addition of trichlorosilane to cyclic olefins

Benkeser, Robert A.; Dunny, Stanley; Li, George S.; Nerlekar, P. G.; Work, Stewart D.

doi:10.1021/ja01009a033

Cited by 15 publications

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“…Speier reported that the hydrosilylation of 2-pentene with certain silicon hydrides in the presence of chloroplatinic acid formed the terminal adducts . Benkeser also found that in the hydrosilylation of cyclic olefins, the recovered cyclic olefin mixture included all possible isomers . A stepwise migration of the double bond down the alkyl chain by progressive hydrogen shifts via the intermediacy of the platinum atom has been proposed …”

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“…4 Benkeser also found that in the hydrosilylation of cyclic olefins, the recovered cyclic olefin mixture included all possible isomers. 5 A stepwise migration of the double bond down the alkyl chain by progressive hydrogen shifts via the intermediacy of the platinum atom has been proposed. 4 We found that in the Pt(acac) 2 -catalyzed photoactivated (350 nm) hydrosilylation of alkynes, if the molar ratio of Et 3 SiH to terminal alkyne, 1-hexyne, was 1:1, normal hydrosilylation products were formed.…”

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Photoactivated Isomerization of Linear Olefins^,

Wang

Neckers

2002

J. Org. Chem.

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The photocatalyzed (350 nm) isomerization of linear olefins catalyzed by platinum(II) bis(acetylacetonato) [Pt(acac)(2)] in the presence of silanes was studied. Catalytic activity depends on the silane. Triphenylsilane is the most reactive silane studied, with more than 98% isomerization of the alkene occurring after 20-min irradiation. There is no concomitant hydrosilylation. The mechanism has been investigated and a metal hydride addition-elimination mechanism proposed.

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Photoactivated Isomerization of Linear Olefins^,

Wang

Neckers

2002

J. Org. Chem.

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Hydrogen Hexachloroplatinate(IV)

Sibi

2001

Encyclopedia of Reagents for Organic Synthesis

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Hydrosilation CatalysisBased in part on the article Hydrosilation Catalysis by John F. Harrod which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Marschner¹

2005

Encyclopedia of Inorganic Chemistry

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The addition of a hydrosilane across an unsaturated molecule is called hydrosilation. This can be catalyzed by a number of reagents among which transition metal compounds are most important. The reaction of a variety of different silanes with alkyl, alkoxy, and halogen substituents is well established. The unsaturated molecules involve alkenes, alkynes, and a huge number of different carbonyl compounds as well as combinations thereof. While hydrosilation of alkenes and alkynes can mainly be seen as a silylation method, the reaction with carbonyl compounds constitutes a formal reduction. Among the used catalyst systems hexachloroplatinic acid in isopropanol (Speier's catalyst) is most frequently used. Mechanistically the transition metal catalyzed reaction of an alkene can be seen as an oxidative addition of the silicon hydrogen bond, followed by the migratory insertion of the coordinated alkene into the metal hydrogen or silicon bond and a final reductive elimination of the alkylsilane. The formation of vinylsilanes through the dehydrogenating silation reaction is a frequently occurring side reaction. Such by‐products are thought to be formed by β‐hydride elimination of an intermediate β‐silylalkyl metal complex. The hydrosilation reaction can promote the transformation of a prochiral (alkene, ketone) to a potentially chiral molecule. It bears potential for asymmetric synthesis, which is currently heavily investigated. The reaction is equally popular for classical organic synthesis as well as for material science tasks such as the chemical bonding of a polymer to a surface.

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The addition of trichlorosilane to cyclic olefins

Cited by 15 publications

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Photoactivated Isomerization of Linear Olefins^,

Photoactivated Isomerization of Linear Olefins^,

Hydrogen Hexachloroplatinate(IV)

Hydrosilation CatalysisBased in part on the article Hydrosilation Catalysis by John F. Harrod which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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The addition of trichlorosilane to cyclic olefins

Cited by 15 publications

References 0 publications

Photoactivated Isomerization of Linear Olefins,

Photoactivated Isomerization of Linear Olefins,

Hydrogen Hexachloroplatinate(IV)

Hydrosilation CatalysisBased in part on the article Hydrosilation Catalysis by John F. Harrod which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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Photoactivated Isomerization of Linear Olefins^,

Photoactivated Isomerization of Linear Olefins^,