Solvent-to-Polymer Chirality Transfer in Intramolecular Stack Structure

Lee, Daehoon; Jin, Young-Jae; Kim, Hyojin; Suzuki, Nozomu; Fujiki, Michiya; Sakaguchi, Toshikazu; Kim, Seog K.; Lee, Wang-Eun; Kwak, Giseop

doi:10.1021/ma300976r

Cited by 110 publications

(81 citation statements)

References 103 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…for HPLC because of their preferred-handed helical conformation [17][18][19][20][21][22][23][24][25][26]. 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].…”

Section: Introductionmentioning

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: Introductionmentioning

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

“…8,9 Until now, optically active poly(diphenylacetylene)s have been prepared by the polymerization of optically active monomers, 813 the introduction of optically active groups into the pendants through a macromolecular reaction, 14 or by solvent chirality transfer. 15,16 These polymers are considered to form a preferred-handed helical conformation in solution because they show characteristic Cotton effects at wavelengths >330 nm, attributed to the absorption of the polyene backbone. However, the number of optically active poly(diphenylacetylene)s bearing polar functional groups reported so far is very limited.…”

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

“…The perfect application of chiral solvation method in preparing optically active σ-conjugated polymers and π-conjugated polyphenylacetylenes gave rise to the possibility of inducing optically active PFs. First, Fujiki et al successfully utilized terpene chirality transfer method to generate serials of CD-and/or CPL-active π-conjugative polymers from the corresponding achiral counterparts ( Figure 5) [67][68][69][70][71]. Meanwhile, many diverse factors, such as tersolvent composition, solvent polarity, polymer molecular weight, alkyl chain length, limonene enantiopurity, solution temperature, clockwise and counter-clockwise stirring, and aggregate size are confirmed to influence the magnitude of the induced CD and/or CPL amplitude.…”

Section: Preparation For Optically Active π-Conjugated Polymermentioning

confidence: 99%

Chiral Solvation Induced Supramolecular Chiral Assembly of Achiral Polymers

Zhang¹,

Zhao²,

Yin³

2017

Molecular Self-Assembly in Nanoscience and Nanotechnology

View full text Add to dashboard Cite

To date, liquid crystal chirality, mechanophysical chirality, circularly polarized photon chirality, gelation and chiral solvation are all feasible candidates to generate optically active polymers and supramolecular chirality when employing achiral molecules as starting substances. Among this, chiral-solvation-induced chirality is one of the dominant methods for construction of chirality from achiral sources, such as achiral poly(n-hexyl isocyanate) (PHIC), π-conjugated polymers, oligo(p-phenylenevinylene), polyacetylenes, σ-conjugated polysilanes and side-chain polymers. Supramolecular chirality is well established through their intra-or inter-molecular noncovalent interactions, such as van der Waals, CH/π, dipole-dipole interactions, hydrogen bonding and metal-ligand coordinating interactions. Compared with the traditional methods, this strategy avoids the use of expensive chiral reagents and also expands the scope towards challenging substrates. This chapter highlights a series of studies that include: (i) the development-historical background of chiral solvent induction strategy; (ii) the chiral-solvation-induced chirality in small molecules and oligomers; and (iii) recent developments in polymers, especially in π-conjugated polymers and σ-conjugated polymers.

show abstract

Solvent-to-Polymer Chirality Transfer in Intramolecular Stack Structure

Cited by 110 publications

References 103 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 Solvation Induced Supramolecular Chiral Assembly of Achiral Polymers

Contact Info

Product

Resources

About