Polymerization of substituted acetylenes and features of the formed polymers

Shiotsuki, Masashi; Sanda, Fumio; Masuda, Toshio

doi:10.1039/c0py00333f

Cited by 267 publications

(177 citation statements)

References 148 publications

Supporting

Mentioning

177

Contrasting

Order By: Relevance

“…The direct polymerization of diphenylacetylene monomers bearing polar functional groups, such as carboxyl and amide groups, hardly proceeds because the group 5 transition metals used for polymerization of disubstituted acetylenes are intolerant to such polar functional groups [37,38]. With this in mind, the carboxyl groups of the diphenylacetylene monomer (1) were protected as the corresponding n-heptyl esters prior to being polymerized in toluene with WCl6-Ph4Sn at 100 °C.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC

et al. 2016

View full text Add to dashboard Cite

A series of optically active poly(diphenylacetylene) derivatives bearing a chiral substituent (poly-2S) or chiral and achiral substituents (poly-(2S x -co-3 1−x )) on all of their pendant phenyl rings were synthesized by the reaction of poly(bis(4-carboxyphenyl)acetylene) with (S)-1-phenylethylamine ((S)-2) or benzylamine (3) in the presence of a condensing reagent. Their chiroptical properties and chiral recognition abilities as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) were investigated. Poly-2S and poly-(2S x -co-3 1−x ) (0.06 < x < 0.71) formed a preferred-handed helical conformation with opposite helical senses after thermal annealing despite possessing the same chiral pendant (h-poly-2S and h-poly-(2S x -co-3 1−x )). Furthermore, h-poly-2S and h-poly-(2S 0.36 -co-3 0.64 ) emitted circularly polarized luminescence with opposite signs. h-Poly-2S showed higher chiral recognition abilities toward a larger number of racemates than poly-2S without a preferred-handed helicity and the previously reported preferred-handed poly(diphenylacetylene) derivative bearing the same chiral substituent on half of its pendant phenyl rings. h-Poly-(2S 0.36 -co-3 0.64 ) also exhibited good chiral recognition abilities toward several racemates, though the elution order of some enantiomers was reversed compared with h-poly-2S.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Poly(diphenylacetylene)s are more stable than the poly(phenylacetylene) counterparts. 17,18 Therefore, we believe that optically active poly(diphenylacetylene)s bearing a polar functional group would provide a promising scaffold for developing practically useful CSPs for HPLC. Various optically active functional groups, such as amide and ester groups, can be introduced through the macromolecular reaction of the precursor polymer bearing a carboxy group with optically active amines and alcohols, respectively, using a condensing agent, which would lead to a CSP with much higher chiral recognition ability toward diverse racemates.…”

mentioning

confidence: 99%

“…10,11,14 This is because group 5 transition metals capable of polymerizing disubstituted acetylenes are sensitive to polar functional groups and the direct polymerization of diphenylacetylene monomers bearing polar functional groups hardly proceed. 17,18 In the present study, we synthesized an optically active poly(diphenylacetylene) derivative bearing an amide group as an effective chiral recognition site by the macromolecular reaction of the optically inactive precursor poly(diphenylacetylene) bearing carboxy groups with an optically active amine (Scheme 1) and investigated its chiral recognition ability as a CSP for HPLC.…”

mentioning

confidence: 99%

Chiral Recognition Ability of an Optically Active Poly(diphenylacetylene) as a Chiral Stationary Phase for HPLC

Maeda¹,

Maruta²,

Shimomura³

et al. 2016

Chem. Lett.

View full text Add to dashboard Cite

An optically active poly(diphenylacetylene) with a pendant amide functional group was synthesized by a macromolecular reaction of the optically inactive poly(diphenylacetylene) bearing carboxy groups with (S)-1-phenylethylamine. The obtained polymer showed good chiral recognition ability towards diverse racemates when used as a chiral stationary phase for highperformance liquid chromatography. The chiral recognition ability was substantially influenced by the chiral conformation, probably preferred-handed helical conformation, which was induced by thermal annealing in dimethylformamide after introducing optically active pendants through the macromolecular reaction.Keywords: Chiral recognition | Poly(diphenylacetylene) | Chiral stationary phaseEnantioseparation by high-performance liquid chromatography (HPLC) is an effective method not only for analyzing enantiomer compositions but also for obtaining pure enantiomers. A large number of chiral stationary phases (CSPs) have been developed to resolve various racemates.

show abstract

“…[1][2][3] Although a large number of singlestranded helical polymers and oligomers have been reported, [2][3][4][5][6][7][8][9][10][11][12] examples of double-stranded helical polymers and oligomers remain relatively scarce. 2,3,8,9,[13][14][15][16][17][18][19][20][21][22] We have recently reported on the rational design and synthesis of a series of complementary double-stranded helical oligomers [23][24][25][26][27][28] with an optical activity that consists of a crescent-shaped m-terphenyl-based backbone containing amidine and carboxylic acid groups.…”

Section: Introductionmentioning

confidence: 99%

Chiral amplification in double-stranded helical polymers through chiral and achiral amidinium–carboxylate salt bridges

Makiguchi

Kobayashi

Furusho

et al. 2012

Polym J

View full text Add to dashboard Cite

A series of m-terphenyl-based random copolymers of chiral and achiral amidines, and their complementary homopolymers of achiral carboxylic acids were prepared by the copolymerization of a p-diiodobenzene derivative, with the diethynyl monomers containing a chiral or achiral amidine group and a carboxyl group using the Sonogashira coupling reaction. The obtained chiral/achiral amidine copolymers assembled into a double-stranded helical structure upon complexation with the complementary achiral homopolymer of carboxylic acids through interstrand amidiniumÀcarboxylate salt bridges. The complexes exhibited characteristic induced cotton effects in the p-conjugated main-chain chromophore regions, indicating that the interstrand duplexes possess a preferred-handed double-helical structure. The effect of the chiral and achiral amidine contents on the amplification of the helical chirality ('the sergeants and soldiers effect') during the interstrand double-helix formation was investigated by comparing the cotton effect patterns and intensities of the duplexes with those of the corresponding all-chiral amidine-based double-helical polymer. Keywords: amidine; carboxylic acid; chirality; chiral amplification; circular dichroism; double helix INTRODUCTIONThe complementary double-helical structure of DNA is a key structural motif for its vital functions in biological systems, such as replication and the storage of genetic information, which has prompted chemists to develop synthetic double-helical polymers and oligomers (foldamers). [1][2][3] Although a large number of singlestranded helical polymers and oligomers have been reported, 2-12 examples of double-stranded helical polymers and oligomers remain relatively scarce. 2,3,8,9,[13][14][15][16][17][18][19][20][21][22] We have recently reported on the rational design and synthesis of a series of complementary double-stranded helical oligomers [23][24][25][26][27][28] with an optical activity that consists of a crescent-shaped m-terphenyl-based backbone containing amidine and carboxylic acid groups. In our design, the formation of the intertwined duplex is driven by the formation of an amidiniumcarboxylate salt bridge, and the helicity of the duplexes can be readily controlled by the introduction of chiral substituents on the nitrogen atoms of the amidine residues. 9,15,18,19 We also reported on mterphenyl-based conjugated polymers, which contain optically active amidine groups (poly-A 1 ) and achiral carboxylic groups (poly-C), that folded into an intertwined double-stranded helical structure through the chiral amidinium-carboxylate salt bridges. 29 In this study, we synthesized a series of m-terphenyl-based random copolymers containing chiral and achiral amidines (poly-A x ) and

show abstract

Polymerization of substituted acetylenes and features of the formed polymers

Abstract: This review summarizes the recent advances of substituted polyacetylene chemistry, including new polymerization catalysts and the properties and functions of the polymers.

Cited by 267 publications

References 148 publications

Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC

Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC

Chiral Recognition Ability of an Optically Active Poly(diphenylacetylene) as a Chiral Stationary Phase for HPLC

Chiral amplification in double-stranded helical polymers through chiral and achiral amidinium–carboxylate salt bridges

Contact Info

Product

Resources

About