Ruthenium-catalyzed hydrosilylation of terminal alkynes: stereodivergent synthesis of (E)- and (Z)-alkenylsilanes

Katayama, Hiroyuki; Taniguchi, Ken; Kobayashi, Masayuki; Sagawa, Takashi; Minami, Tatsuya; Ozawa, Fumiyuki

doi:10.1016/s0022-328x(01)01319-5

Cited by 98 publications

(37 citation statements)

References 27 publications

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“…This reaction has recently been applied to the stereocontrolled synthesis of poly(p -phenylenevinylene)s by Ozawa and Katayama [8]. They also reported that alkenyl [3,5-bis(trifluoromethyl)phenyl]silanes and alkenyl(4-trifluoromethylphenyl)silanes are also effective [9]. Denmark demonstrated that alkneylsilacyclobutanes are excellent coupling partners [10].…”

mentioning

confidence: 99%

Triallyl(aryl)silanes serve as a convenient agent for silicon-based cross-coupling reaction of aryl halides

Nakao

Oda

Sahoo

et al. 2003

Journal of Organometallic Chemistry

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confidence: 99%

Triallyl(aryl)silanes serve as a convenient agent for silicon-based cross-coupling reaction of aryl halides

Nakao

Oda

Sahoo

et al. 2003

Journal of Organometallic Chemistry

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“…-catalyzed E-selective hydrosilylation of terminal alkynes was previously reported for small molecules by Ozawa et al [44] We transferred the reported reaction conditions to mesogenic phenyl acetylene derivatives. This strategy allowed the synthesis of mesogen end capped disiloxanes 14 and 18 and mesogen-decorated cyclotetrasiloxanes 28.…”

Section: IImentioning

confidence: 98%

“…[44] To a solution of the phenyl acetylenes 8 a,b (2.5 mmol) in dry CH 2 Cl 2 (40 mL) was added 0.03 equiv of the catalyst [RuCl(CO)H(PPh 3 ) 3 ]. Subsequently octamethylcyclotetrasiloxane (10, 0.625 mmol) was added with a syringe.…”

Section: 3-di-((ementioning

confidence: 99%

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Self‐Assembly of Linear and Cyclic Siloxane‐Containing Mesogens: Investigation of Layered Structures in Bulk and Thin Films

et al. 2011

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Silicon-containing materials which possess the ability to form mesophases are promising systems for applications in the fields of electro-optical devices, nonlinear optics, and information storage media. In this work, the formation of supramolecular assemblies of a series of low molecular weight siloxane-containing mesogens is presented. Besides a novel synthesis route via Ru(II) -catalyzed hydrosilylation of phenyl acetylene derivatives, mesophase characterization by modern analysis techniques is performed. As linker groups, leading to bi- and tetramesogens, linear disiloxane and cyclic tetrasiloxane are utilized. In the resulting class of materials, high thermal stability, induced by the formation of layered smectic-type structures, is predominant. The smectic-type phases were found to be monotropic. Layer distances in the assemblies, as well as the phase transition temperatures, can be controlled by the substitution motif on the mesogens (number and length of alkyl chains). In spin-cast thin films, the layered domains are visualized by atomic force microscopy; furthermore, domain dimensions and electron densities are determined by grazing-incidence small-angle X-ray scattering.

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“…Ozawa and coworkers have shown that the hydrosilylation of terminal alkynes (RC ≡ CH; R = Ph, p -tolyl, Cy and n -hexyl) with a number of hydrosilanes can be affected in a stereodivergent manner by small changes in the Ru -catalyst structure (Scheme 15.11 ) [63] . Catalytic amounts of RuHCl(CO)(PPh 3 ) 3 gave ( E ) -β -vinyl silanes ( > 99% selectivity) whereas Ru(SiMe 2 Ph)Cl(CO)(P -i -Pr 3 ) 2 gave ( Z ) -β -vinyl silanes (99% selectivity).…”

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confidence: 99%

Alkyne Reductions

Munslow¹

2008

Modern Reduction Methods

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15 IntroductionAlkynes are highly versatile building blocks for organic chemists due to the ease with which they can be modifi ed. The selective semi -hydrogenation of alkynes is an important process for the fi ne chemical industry, manufacturing of insect sex pheromones and vitamins [1] , and for industrial polymerization processes, where removal of alkynes from alkene feedstocks is crucial [2] . The hydrometallation of alkynes is perhaps the most straightforward method for the production of vinylmetal intermediates. Vinylmetal reagents are important organic intermediates that can function in oxidation and reduction reactions as nucleophiles or in Pdcatalyzed cross -coupling reactions.This chapter covers three methods for alkyne reductions: hydrogenation [3, 4] , hydroboration [5] and hydrosilylation [6] . For the hydroalumination and hydromagnesiation of alkynes, the reader is directed to the relevant sections in Chapter 18 . Their reduction with dissolved metals is discussed in Chapter 17 . Also of interest, but not discussed here, are the hydrometallation reactions including hydrostannation [7] , hydrogermylation [8] and hydroselenation [9] . HydrogenationThe addition of molecular hydrogen (H 2 ) to carbon -carbon multiple bonds has been studied extensively and is a technique frequently used by chemists [10] . The partial reduction of alkynes gives alkenes, whereas total reduction gives alkanes. Total reduction can be simply achieved by catalytic hydrogenation. Alkanes are easily obtained with palladium [11] , Raney nickel [12] or Adams ' platinum oxide [13] under low pressures of hydrogen. A number of alkynes have been fully reduced with the complexes [RhCl(PPh 3 ) 3 ] and [Ru(OAc)(PPh 3 ) 3 ] [14] . The electronrich titanium complexes [Cp 2 Ti(PhC ≡ CPh)(PMe 3 )], [(MeCp) 2 Ti(PhC ≡ CPh)(PMe 3 )]

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Ruthenium-catalyzed hydrosilylation of terminal alkynes: stereodivergent synthesis of (E)- and (Z)-alkenylsilanes

Cited by 98 publications

References 27 publications

Triallyl(aryl)silanes serve as a convenient agent for silicon-based cross-coupling reaction of aryl halides

Triallyl(aryl)silanes serve as a convenient agent for silicon-based cross-coupling reaction of aryl halides

Self‐Assembly of Linear and Cyclic Siloxane‐Containing Mesogens: Investigation of Layered Structures in Bulk and Thin Films

Alkyne Reductions

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