Living Polymerization of Phenylacetylenes Initiated by Rh(C.tplbond.CC6H5)(2,5-norbornadiene)[P(C6H5)3]2

Kishimoto, Y.; Eckerle, Peter; Miyatake, Tatsuya; Ikariya, Takao; Noyori, Ryoji

doi:10.1021/ja00105a095

Cited by 231 publications

(154 citation statements)

References 2 publications

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“…13,14 The living polymerization of 1 was first accomplished by Noyori and coworker in 1994. 63 The excellent ability of an isolated catalyst, (Ph 3 P) 2 (nbd)Rh-C:C-Ph, to achieve quantitative yields of poly(phenylacetylenes) with narrow MWD (M w /M n $ 1.1) in the presence of 4-(N,N-dimethylamino)pyridine (DMAP) was demonstrated. It was disclosed that the initiation reaction proceeds not via direct insertion of monomer into the Rh complex but through the formation of a Rh-H complex by the reaction of the Rh complex with monomer followed by monomer insertion.…”

Section: Rh-based Living Polymerization Catalystsmentioning

confidence: 99%

Substituted polyacetylenes

Masuda

2006

J. Polym. Sci. A Polym. Chem.

389

222

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This article reviews the chemistry of substituted polyacetylenes developed by our research group, more specifically, development of polymerization catalyst, synthesis of new polymers, elucidation of their structure, investigation of their properties, and development of their functions. The main features are as follows: a number of catalysts based on group 5, 6, and 9 transition metals (Nb, Ta, Mo, W, and Rh) have been developed, which include living polymerization catalysts. By using these catalysts, many new substituted polyacetylenes have been synthesized, whose molecular weights are very high (Mw = 104−106). Most of the polymers are soluble in many common solvents and stable enough in the air unlike polyacetylene. Some of these polymers exhibit interesting functions including high gas permeability and photoelectronic properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 165–180, 2007

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Section: Rh-based Living Polymerization Catalystsmentioning

confidence: 99%

Substituted polyacetylenes

Masuda

2006

J. Polym. Sci. A Polym. Chem.

389

222

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“…Cis-Poly(phenylacetylene) (cis-PPA) was synthesized using a Rh(C'COC 6 H 5 ) {Ph 3 P} 2 catalyst reported by Noyori et al 16 The number-average molecular weight (M n ) and molecular weight distribution (M w /M n ) of PPA, which were determined from gel permeation chromatogram (GPC) using poly(styrene) as the standard, were 25,000 and 1.76, respectively. The 80°-deflected transpoly(phenylacetylene) (deflected trans-PPA) was prepared in the following way.…”

Section: Experimental Samplementioning

confidence: 99%

Cis-trans isomerization and13C-NMR chemical shift of polyphenylacetylene

Ishii

Matsunami

Shibata

et al. 1999

J. Polym. Sci. B Polym. Phys.

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“…7 The stereoregularity of the obtained polymer was confirmed to be almost completely cis-transoidal by 1 H NMR analysis ( Figure S1). 8,9 The number-average molecular weight and its distribution, determined by size-exclusion chromatography, were 9.4 © 10 5 and 1.7, respectively. Poly(BCBA) was totally insoluble in nhexane, but soluble in toluene and chiral alcohol 1, whereas the previously reported poly(DOBA) was soluble in n-hexane and insoluble in 1.…”

mentioning

confidence: 98%

Macromolecular Helicity Induction and Memory in a Poly(biphenylylacetylene) Bearing an Ester Group and Its Application to a Chiral Stationary Phase for High-performance Liquid Chromatography

et al. 2015

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An optically inactive poly(biphenylylacetylene) bearing an ester group at the 4¤-position of the pendants formed a preferredhanded helical conformation and biased axial chirality in the pendants through a noncovalent interaction with a chiral alcohol, both of which were retained (memorized) even after removal of the chiral alcohol. The chiral stationary phase for high-performance liquid chromatography, prepared by coating the polymer with macromolecular helicity memory on silica gel, showed good chiral recognition ability towards various racemates.Direct enantioseparation, using chiral stationary phases (CSPs), by high-performance liquid chromatography (HPLC) has provided a promising method not only for performing microanalysis of chiral compounds but also for obtaining highly-pure enantiomers on the ton scale.1,2 Although a large number of CSPs have been developed, 3,4 it is still a challenging issue to switch the elution order of enantiomers without using the CSPs prepared from antipodal chiral materials despite their advantages both in analytical and preparative modes. 5,6 We recently reported that poly([2,2¤-bis(methoxymethoxy)-4¤-dodecyloxy-4-biphenylyl]acetylene) (poly(DOBA)) forms a preferred-handed helical conformation together with an excess of one of the axially twisted conformations in the biphenyl pendants, which occurs through the noncovalent interaction with an optically active alcohol ((R)-or (S)-1) both in solution and in the solid state. 7 The induced main-chain helicity and axial chirality can be maintained (or memorized) even after the removal of the chiral alcohol (Scheme 1). By using this unusual feature of poly(DOBA), we succeeded in developing a switchable CSP in which the elution order of the enantiomers could be switched at will on the basis of reversible switching and the subsequent memory of macromolecular helicity in poly(DOBA) by sequential treatment with (R)-and (S)-1 in the solid state.However, the chiral recognition ability of poly(DOBA) was not high. In this communication, we designed and synthesized a novel cis-transoidal poly(biphenylylacetylene) derivative bearing an ester group as an effective chiral recognition site instead of an ether group, poly([2,2¤-bis(methoxymethoxy)-4¤-butoxycarbonyl-4-biphenylyl]acetylene) (poly(BCBA)) (Scheme 1), and investigated the effects of the functional group at the 4¤-position of the biphenyl pendant on helicity induction and memory effect, and further the chiral recognition ability as a CSP for HPLC.Poly(BCBA) was synthesized by the polymerization of the corresponding biphenylylacetylene monomer (Scheme S1) with a rhodium catalyst ([Rh(nbd)Cl] 2 ; nbd: norbornadiene) in tetrahydrofuran in the presence of triethylamine in a similar method to that previously reported (Scheme S2).7 The stereoregularity of the obtained polymer was confirmed to be almost completely cis-transoidal by 1

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Living Polymerization of Phenylacetylenes Initiated by Rh(C.tplbond.CC6H5)(2,5-norbornadiene)[P(C6H5)3]2

Cited by 231 publications

References 2 publications

Substituted polyacetylenes

Substituted polyacetylenes

Cis-trans isomerization and13C-NMR chemical shift of polyphenylacetylene

Macromolecular Helicity Induction and Memory in a Poly(biphenylylacetylene) Bearing an Ester Group and Its Application to a Chiral Stationary Phase for High-performance Liquid Chromatography

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