Enantioselective sensing of chiral amino alcohols with a stereodynamic arylacetylene‐based probe

Iwaniuk, Daniel P.; Bentley, K. W.; Wolf, Christian

doi:10.1002/chir.22066

Cited by 23 publications

(11 citation statements)

References 59 publications

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“…9). [32][33][34] These probes exist as a CD silent mixture of rapidly interconverting achiral and chiral conformations due to ''frictionless'' rotation about the alkyne bonds. The orientation of the benzaldehyde rings and the length of the two branches and the central rod of this fully conjugated probe were carefully chosen to maximize substrate-controlled induction of axial chirality and strong CD output upon condensation with a variety of amines or amino alcohols.…”

Section: Imine Foldamersmentioning

confidence: 99%

Chirality sensing using stereodynamic probes with distinct electronic circular dichroism output

2013

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Circular dichroism (CD) spectroscopy is one of the most useful techniques for the stereochemical analysis of chiral biopolymers and fine chemicals. It has become invaluable for the assignment of the absolute configuration, the study of conformational isomers, and the determination of racemization kinetics of CD active chiral compounds. Molecular interactions between a nonracemic chiral substrate and a chromophoric, CD-silent probe that is achiral or exists as a racemic mixture of rapidly interconverting enantiomeric conformations or configurations can induce a strong, characteristic chiroptical readout. A covalent or noncovalent binding event that coincides with a well-defined asymmetric induction process can effectively imprint the chiral information of the substrate on the stereodynamic sensor and thus generate intense Cotton effects in the UV region of the latter. The probe can thus function as a stereochemical reporter unit and analysis of the CD spectrum often provides accurate information about the absolute configuration and enantiomeric composition of the substrate used. In this review, recent developments in circular dichroism analysis of chiral compounds with stereodynamic probes are described and particular emphasis is given to sensor design, chiral induction processes and applications scope.

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Section: Imine Foldamersmentioning

confidence: 99%

Chirality sensing using stereodynamic probes with distinct electronic circular dichroism output

2013

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“…The fundamental characteristics are already present in bridgedb iphenyls:a na lkyl linker bridges the phenyl rings, which locks them in as pecific conformation (M or P). [16][17][18][19][20][21][22] Adding at hird ring (also conformationally locked by an alkyl bridge)r esultsi nV çgtle's terphenylic Geländer-oligomers. The obtained structures show very similar chiroptical properties and conformational stability to those of shorter helicenes.…”

Section: Introductionmentioning

confidence: 99%

Tuning Helical Chirality in Polycyclic Ladder Systems

Rickhaus

Unke

Mannancherry

et al. 2015

Chemistry A European J

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Conceptually and experimentally, a new set of helical model compounds is presented herein that allow correlations between structural features and their expression in the secondary structure to be investigated. A cross-linked oligomer with two strands of mismatching lengths connected in a ladder-type fashion serves as a model system. Compensation for the dimensional mismatch leads to the adoption of a helical arrangement. A strategically placed relay ensures the continuity and uniformity of the helix. Upon exchanging the heteroatomic linkage, the helix responds by increasing or decreasing the torsion of the backbone. Inversion of the relay's substitution pattern causes a distortion of the structure, while maintaining the directionality of the helix. Based on a short synthetic protocol with a modular precursor, four closely related "Geländer" oligomers (Geländer is the German word for bannister) were accessed and fully characterized. XRD analysis for one representative of each helical arrangement and complementary computational studies for the remaining derivatives allowed the impact of the alterations on the secondary structures to be studied. Isolation of pure enantiomers of all new Geländer oligomers provided insight into the racemization kinetics and estimation of the racemization barrier. In silico simulation of the electronic circular dichroism spectra of the model compounds enabled the helicity of the isolated samples to be assigned.

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“…29 For example, the groups of Anslyn and Wolf have developed and tested CD methods for the analysis of chiral analytes including amino acids 30 , alcohols, 31 amino alcohols 32,33 carboxylates 34 and amines. 35-38 Biological/biochemical sciences may benefit likewise.…”

Section: Introductionmentioning

confidence: 99%

Well plate circular dichroism reader for the rapid determination of enantiomeric excess

et al. 2014

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Circular dichroism (CD) spectropolarimeters typically employ one photoelastic modulator. However, spectropolarimeters employing two or even four modulators are more versatile and can be used to subvert common measurement errors arising from imperfectly isotropic samples or sample holders. Small linear anisotropies that can cause large errors in CD measurement can be associated with multi-well sample holders. Thus, high-throughput CD analyses in multi-well plates have not yet been demonstrated. One such application is the determination of enantiomeric excess of a library of reaction products. Herein, a spectropolarimeter employing four photoelastic modulators and a translation stage was used to determine the enantiomeric excess of a family of chiral amine complexes much more rapidly than could be achieved with a robotic fluid injection system. These experiments are proof of concept for high-throughput CD analysis. In practice, commercially available glass bottomed well plates are sufficiently strain free such that a simple instrument with just one photoelastic modulator and a vertical optical train should be able to deliver the CD without special considerations given herein. On the other hand, polystyrene well plates cannot be used in this way.

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Enantioselective sensing of chiral amino alcohols with a stereodynamic arylacetylene‐based probe

Cited by 23 publications

References 59 publications

Chirality sensing using stereodynamic probes with distinct electronic circular dichroism output

Chirality sensing using stereodynamic probes with distinct electronic circular dichroism output

Tuning Helical Chirality in Polycyclic Ladder Systems

Well plate circular dichroism reader for the rapid determination of enantiomeric excess

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