Functionalization of vinyl-substituted linear oligo- and polysiloxanes via ruthenium catalyzed silylative coupling with styrene

Żak, Patrycja; Skrobańska, Monika; Pietraszuk, Cezary; Marciniec, Bogdan

doi:10.1016/j.jorganchem.2009.01.028

Cited by 11 publications

(2 citation statements)

References 22 publications

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“…Silylative coupling in the presence of ruthenium complexes has also been successfully applied to the functionalization of multivinyl-substituted organosilicon compounds such as cyclosiloxanes and cyclosilazanes, 21,22 silsesquioxanes and spherosilicates 23,24 as well as to the modification of vinyl-substituted polysiloxanes. 25 Functionalized polyhedral silsesquioxanes (POSS) and spherosilicates have attracted widespread…”

Section: Grzegorz Hreczychomentioning

confidence: 99%

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

2015

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The development of highly selective methods for the synthesis of functionalized olefins, based on sequential catalytic reactions of organometallic reagents, has been the subject of extensive study because of their versatile applications in organic synthesis and materials science. The silylative coupling of olefins with vinyl-substituted organosilicon compounds (discovered in our group) represents one of the most efficient and straightforward methods for the synthesis of stereodefined alkenylsilanes and bis (silyl) alkenes, which are particularly attractive scaffolds for further transformations including palladium-catalyzed cross-coupling with organic halides (Hiyama coupling) or electrophile-induced desilylation. The article highlights the recent developments and covers the literature mainly from the last decade in the sequential (also one-pot) synthetic strategies including ruthenium-catalyzed silylative coupling followed by desilylative cross-coupling, acylation and halogenation, leading to stereodefined organic derivatives such as (E)-alkenyl halides, (E)-α,β-unsaturated ketones or arylene-(E)-vinylene derivatives which are widely applied as fine chemicals, functional materials or building blocks in organic synthesis. † Dedicated to Prof. Ei-ichi Negishi on the occasion of his 80th birthday.

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Section: Grzegorz Hreczychomentioning

confidence: 99%

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

2015

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“…[6] The silylative coupling of olefins with vinylsilanes proceeds according to a mechanism involving the activation of =C À H and Si À C= bonds (Scheme 1) and is catalysed by complexes containing or generating hydride ([M]-H) or silyl ([M]-Si) ligands (silicometallics) (where M = Ru, Rh, Ir, Co). [7] A wide variety of vinylsubstituted silanes, [2] cyclosiloxane trimers [8] and tetramers [9] and, recently, linear vinyl-substituted oligoand polysiloxanes [10] have been effectively functionalised via silylative coupling with styrene and some other olefins in the presence of ruthenium hydride complexes, e.g.,…”

Section: Introductionmentioning

confidence: 99%

Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross‐Metathesis and Silylative Coupling with Olefins in the Presence of Ruthenium Complexes

et al. 2009

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Monovinylheptaisobutylsilsesquioxane undergoes efficient cross-metathesis and silylative coupling with styrenes. Allyl derivatives were successfully tested in cross-metathesis in the presence of first generation Grubbs catalyst, while heteroatom-substituted vinyl derivatives (vinyl ethers, 9-vinylcarb-A C H T U N G T R E N N U N G azole) efficiently undergo silylative coupling catalysed by ruthenium hydride complexes. Both reactions proceed highly stereoselectively and lead to nearly quantitative formation of E isomers. Only when vinyl ethers are used does the reaction lead to a mixture of stereoisomers. Atmospheric pressure photoA C H T U N G T R E N N U N G ionisation has been successfully used for recording mass spectra of the functionalised silsesquioxanes.

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Metathesis of Silicon‐Containing Olefins

Pietraszuk¹,

Pawluć²,

Marciniec³

2015

Handbook of Metathesis

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Functionalization of vinyl-substituted linear oligo- and polysiloxanes via ruthenium catalyzed silylative coupling with styrene

Cited by 11 publications

References 22 publications

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross‐Metathesis and Silylative Coupling with Olefins in the Presence of Ruthenium Complexes

Metathesis of Silicon‐Containing Olefins

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