Stereocontrolled synthesis of (E)- and (Z)-poly(p-phenylenevinylene)s via ruthenium-catalyzed hydrosilylation of p-diethynylbenzene

Katayama, Hiroyuki; Nagao, Masato; Moriguchi, Rie; Ozawa, Fumiyuki

doi:10.1016/s0022-328x(03)00266-3

Cited by 42 publications

(23 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Synthesis and Characterization of PmPVs. All-cis and alltrans PmPVs were synthesized by Suzuki-Miyaura-type 2,7 and Hiyama-type polycondensations, 8,9 respectively (Scheme 1). The choice of catalytic cross-coupling reactions dependent on desirable stereochemistry is based on our previous findings on PpPVs synthesis.…”

Section: Resultsmentioning

confidence: 99%

“…All-cis and all-trans PmPVs were synthesized by Suzuki−Miyaura-type , and Hiyama-type polycondensations, , respectively (Scheme ). The choice of catalytic cross-coupling reactions dependent on desirable stereochemistry is based on our previous findings on PpPVs synthesis. , The inverse use of the reactions often causes structural defects in resulting polymers.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Stereocontrolled Synthesis and Photoisomerization Behavior of All-Cis and All-Trans Poly(m-phenylenevinylene)s

2010

Self Cite

View full text Add to dashboard Cite

All-cis and all-trans isomers of poly[(arylenevinylene)-alt-(5-octyloxy-1,3-phenylenevinylene)]s having three kinds of arylene groups (PmPVs: arylene = m-phenylene (1a), p-phenylene (1b), 4,4 0 -biphenylene (1c)) have been synthesized in almost perfect stereoregularity by two types of palladium-catalyzed polycondensation reactions, respectively. Suzuki-Miyaura-type polycondensation of (Z,Z)-bis(2-bromoethenyl)arenes with 5-octyloxy-1,3-benzenediboronic acid pinacolate affords all-cis 1a-c, whereas Hiyama-type polycondensation of (E,E)-bis(2-silylethenyl)arenes with 5-octyloxy-1,3-diiodobenzene forms all-trans 1a-c. The resulting polymers with relatively short effective π-conjugation lengths interrupted by mphenylene units undergo two-way photoisomerization to give PmPVs containing cis-and trans-vinylene groups in nearly 1:1 ratios irrespective of the arylene groups of staring polymers.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Stereocontrolled Synthesis and Photoisomerization Behavior of All-Cis and All-Trans Poly(m-phenylenevinylene)s

2010

Self Cite

View full text Add to dashboard Cite

show abstract

“…Unexpectedly, the anti hydrosilylation of 10 and 10' proved to be much more complicated. In our hands, none of the stereodivergent conditions described by the groups of Faller ([RhCl 2 A C H T U N G T R E N N U N G (Cp*)] 2 , CH 2 Cl 2 ), [25] Ozawa ([RuCl(CO)- [26] [27] led to the desired (1Z,3E)-dienylsilanes 9 and 9'. In all cases, mixtures of stereoisomers were obtained, which we attributed to isomerization of the initially produced Z vinylsilanes through an insertion-b-elimination mechanism in the presence of a catalytic amount of hydrosilane and the Rh or Ru catalysts.…”

Section: Resultsmentioning

confidence: 66%

“…( B I N A P= 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) formed the (E)-vinylsilanes. Ozawa and co-workers [26] reported that the reaction of an alkyne with a hydrosilane containing aromatic substituents led to the correspond- )] was used. Still more remarkably, Mori and co-workers [27] have found that whether [RhI-A C H T U N G T R E N N U N G (PPh 3 ) 3 ] affords (E)-or (Z)-alkenylsilanes (in both cases with excellent stereoselectivity) depends simply on the order of addition of the reagents and the reaction conditions: when the alkyne is added to a mixture of hydrosilane and the catalyst, (Z)-alkenylsilanes are obtained, whereas adding the catalyst to a mixture of the silane and alkyne and then heating at 60 8C affords E products.…”

Section: Resultsmentioning

confidence: 99%

“…In fact, by changing their ligands, Rh and Ru can be "tuned" to afford either diastereomer. [25,26] Faller and DAlliessi [25] found that although the neutral rhodium dimer [(Cp*RhCl 2 ) 2 ] (Cp*= pentamethylcyclopentadienyl) promoted the atypical anti addition of trialkyl-and trialkoxy-substituted silanes to acetylene, yielding the Z isomers, the dicationic complex…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

Bergueiro

Montenegro

Cambeiro

et al. 2012

Chemistry A European J

View full text Add to dashboard Cite

This paper presents a full account of the use of Hiyama cross-coupling reactions in a highly convergent approach to retinoids in which the key step is construction of the central C10-C11 bond. Representatives of two families of oxygen-activated dienyl silanes (ethoxysilanes and silanols) and of all reported families of "safety-catch" silanols (siletanes, silyl hydrides, allyl-, benzyl-, aryl-, 2-pyridyl- and 2-thienylsilanes) were regio- and stereoselectively prepared and stereospecifically coupled to an appropriate electrophile by treatment with a palladium catalyst and a nucleophilic activator. Both all-trans and 11-cis-retinoids, and their chain-demethylated analogues, were obtained in good yields regardless of the geometry (E/Z) and of the steric congestion in each fragment. This comprehensive study conclusively establishes the Hiyama cross-coupling reaction, with its mild reaction conditions and stable, easily prepared, ecologically advantageous silicon-based coupling partners, as the most effective route to retinoids reported to date.

show abstract

Cross‐Coupling with Organosilicon Compounds

et al. 2011

View full text Add to dashboard Cite

Organosilicon functions possess many properties that make them ideal donors of organic groups in cross‐coupling reactions. Through the addition of an appropriate silicophilic Lewis base, an in situ pentacoordinate silane can effectively transfer an organic group. This feature allows for the rapid development of silicon cross‐coupling methods that continue today. Organosilicon‐based cross‐coupling has now become a practical, viable, and in some cases, superior compared with organoboron,‐zinc,‐tin couplings. The unique properties of organosilicon compounds provide a number of distinct advantages to their use as donors in transition‐metal catalyzed cross‐coupling reactions: 1, silicon moieties can be introduced into organic substrates by many general and high‐yielding methods for the construction of silicon carbon bonds; 2, organosilicon reagents are chemically robust and allow isolation and purification of products and are compatible with many functional groups; 3, silicon‐containing by‐products of the coupling are of low molecular weight, are nontoxic, and are easily removed from the reaction mixture; 4, a number of mild methods are available. This chapter presents a thorough overview of the various combinations of transferable groups and organic electrophiles. The scope is limited to the combination of silicon‐bearing nucleophiles with halo or related electrophiles under catalysis by palladium or nickel complexes wherein the silyl halide is lost.

show abstract

Stereocontrolled synthesis of (E)- and (Z)-poly(p-phenylenevinylene)s via ruthenium-catalyzed hydrosilylation of p-diethynylbenzene

Cited by 42 publications

References 27 publications

Stereocontrolled Synthesis and Photoisomerization Behavior of All-Cis and All-Trans Poly(m-phenylenevinylene)s

Stereocontrolled Synthesis and Photoisomerization Behavior of All-Cis and All-Trans Poly(m-phenylenevinylene)s

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

Cross‐Coupling with Organosilicon Compounds

Contact Info

Product

Resources

About