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

Maeda, Katsuhiro; Maruta, Miyuki; Shimomura, Koichiro; Ikai, Tomoyuki; Kanoh, Shigeyoshi

doi:10.1246/cl.160542

Cited by 45 publications

(46 citation statements)

References 22 publications

(23 reference statements)

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“…Moreover, h-poly-2S resolved racemates 8 and 9, which were barely separated on poly-2S. These results therefore indicated that the preferred-handed helical conformation induced in h-poly-2S was playing an important role in its excellent chiral recognition ability, which was consistent with the results of our previous report for h-poly-4S [36]. As expected, poly-2S and h-poly-2S both exhibited higher enantioselectivities toward nine of the racemates than our previously reported poly-4S and h-poly-4S systems, respectively, bearing the same (S)-2 unit on half of their phenyl pendants [36].…”

Section: Resultssupporting

confidence: 91%

“…These results indicated that a predominantly one-handed helical conformation was induced in the polymer backbone by thermal annealing owing to the effect of the optically active pendants (h-poly-2S). A similar thermal annealing was necessary for poly-4S to form the preferred-handed helical conformation (h-poly-4S) [27,36]. This result was attributed to steric hindrance between the neighboring pendant phenyl rings, which was large enough to prevent poly-2S and poly-4S from being transformed into their preferred-handed helical conformations after the introduction of the optically active pendants.…”

Section: Resultsmentioning

confidence: 98%

“…The complete removal of the n-heptyl esters was confirmed by 1 H-NMR and IR spectroscopy ( Figures S1 and S2). Poly-2S was prepared in a similar manner to that previously reported for poly-4S [36], by the polymer reaction of poly-1-H with (S)-2 using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) as a condensing reagent. The near complete introduction of the (S)-2 residue was confirmed by 1 H NMR, IR and elemental analyses ( Figures S1 and S3).…”

Section: Resultsmentioning

confidence: 99%

“…This result was attributed to steric hindrance between the neighboring pendant phenyl rings, which was large enough to prevent poly-2S and poly-4S from being transformed into their preferred-handed helical conformations after the introduction of the optically active pendants. conformation (h-poly-4S) [27,36]. This result was attributed to steric hindrance between the neighboring pendant phenyl rings, which was large enough to prevent poly-2S and poly-4S from being transformed into their preferred-handed helical conformations after the introduction of the optically active pendants.…”

Section: Resultsmentioning

confidence: 99%

“…However, very few optically active poly(diphenylacetylene)s have been prepared to date, which has limited research towards evaluating the scope and efficiency of the chiral recognition abilities of these materials [27][28][29][30][31][32][33][34][35]. We recently reported the first example of an optically active poly(diphenylacetylene)-based CSP for HPLC [36]. In this particular case, we synthesized an optically active poly(diphenylacetylene) bearing a chiral pendant amide moiety (poly-4S) (Figure 1) by the reaction of an optically inactive precursor polymer bearing a pendant carboxyl group with the optically active amine (S)-1-phenylethylamine (S)-2.…”

Section: Introductionmentioning

confidence: 99%

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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

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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.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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

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Supramolecular chiral polymeric aggregates: Construction and applications

et al. 2022

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Inspired by the mystery of natural homochirality, the design and construction of artificial chiral systems with special functions including mechanics, chiroptical devices, and chiral separation have aroused the great interest of scientists. Due to its diverse conformations and components, polymers become an excellent candidate to construct artificial chiral aggregates, which provides an opportunity to fabricate advanced chiral materials. Herein, in this review, we summarized not only the different strategies for construction and regulation of supramolecular chirality in chiral or achiral polymer systems, mainly including post-assembly and polymerizationinduced chiral self-assembly in chiral polymer systems and several chirality transfer and induction strategies in achiral polymer systems, but also the formation mechanisms of chiral aggregates by the chirality amplification from the molecular level to supramolecular level. Furthermore, we present the typical applications of chiral polymeric aggregates in circularly polarized light emission, chiral recognition and separation, and chiral elastomer. Finally, the current challenges and future directions of chiral polymeric aggregates are also elaborated. K E Y W O R D S aggregates, chiral applications, chiral assembly, chirality, polymers INTRODUCTION OF CHIRALITY Chirality in diverse scalesIn nature, chiral structures are widespread at various hierarchical levels, such as the chiral amino acid molecules, the double-helical structure of DNA biomacromolecules, the helical shape of bacterial flagella, and even the visible plant cane and galaxy (Figure 1). [1,2] Scientists have also been working on mimicking helical phenomena in nature and exploring the mechanism of chiral information transfer and amplification, so as to reveal the origin of life and develop advanced functional materials. [3][4][5][6] According to the assembling structures of chiral substances at the molecular level and above, chirality can generally be divided into molecular chirality, supramolecular chirality, and macrochirality, which isThis is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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Revisiting the Polymerization of Diphenylacetylenes with Tungsten(VI) Chloride and Tetraphenyltin: An Alternative Mechanism by a Metathesis Catalytic System

et al. 2020

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An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism.

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

Cited by 45 publications

References 22 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

Supramolecular chiral polymeric aggregates: Construction and applications

Revisiting the Polymerization of Diphenylacetylenes with Tungsten(VI) Chloride and Tetraphenyltin: An Alternative Mechanism by a Metathesis Catalytic System

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