Point-to-Axial Chirality Transmission: A Highly Sensitive Triaryl Chirality Probe for Stereochemical Assignments of Amines

Mądry, Tomasz; Czapik, Agnieszka; Kwit, Marcin

doi:10.1021/acs.joc.0c00734

Cited by 5 publications

(5 citation statements)

References 80 publications

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“…As it has been reported previously, the initial attempts to the modification of the 2,5-di(1-naphthyl)terephthalaldehyde probe by replacing the naphthalene with other chromophore (preferably anthracene) failed [30]. However, we successfully synthesized the derivative 1 of the modular structure by Suzuki coupling of 2,5-dibromoterephthalaldehyde with 2-biphenylboronic acid (all details regarding synthesis and full spectroscopic characterization of the compounds are contained in the Supplementary Information) [39].…”

Section: Resultsmentioning

confidence: 96%

“…The numerical UV and ECD data are juxtaposed in Table 1, and in Figure 7, example ECD spectra of imines 2a, 2c, 2f, and 2h are shown. For the sake of comparison, in Figure 7, we additionally show the ECD spectra of the corresponding imines obtained from 2,5-di(1-naphthyl)terephthalaldehyde and (R)-2-aminebutane, (R)-2-amine-3,3-dimethylbutane, (R)-3-aminetetrahydrofurane, and (R)-1-phenylethylamine (data taken from [30]).…”

Section: Chirogenesis In Imines 2a-2kmentioning

confidence: 99%

“…Recently, we have proven that the ECD-silent chromophoric probe, based on the 2,5-di(1-naphthyl)terephthalaldehyde skeleton, might be efficiently applied for chirality sensing of primary amines through the point-to-axial chirality transmission mechanism [30]. A feature that distinguishes this probe from others is unprecedentedly high sensitivity to subtle differences in the inductor structure.…”

Section: Introductionmentioning

confidence: 99%

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“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

2021

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The electronic circular dichroism (CD)-silent 2,5-bis(biphen-2-yl)terephthalaldehyde has been used as a sensor (reporter) of chirality for primary amines. The through-space inductor–reporter interactions force a change in the chromophore conformation toward one of the diastereomeric forms. The structure of the reporter, with the terminal flipping biphenyl groups, led to generating Cotton effects in both lower- and higher-energy regions of the ECD spectrum. The induction of an optical activity in the chromophore was due to the cascade point-to-axial chirality transmission mechanism. The reporter system turned out to be sensitive to the subtle differences in the inductor structure. Despite the size of the chiral substituent, the molecular structure of the inductor–reporter systems in the solid-state showed many similarities. The most important one was the tendency of the core part of the molecules to adapt pseudocentrosymmetric conformation. Supported by a weak dispersion and Van der Waals interactions, the face-to-face and edge-to-face interactions between the π-electron systems present in the molecule were found to be responsible for the molecular arrangement in the crystal.

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Section: Resultsmentioning

confidence: 96%

Section: Chirogenesis In Imines 2a-2kmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

2021

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“…Thus, a pseudo-axial chirality is induced in the dyads by the stereogenic center of the chiral side chains upon intramolecular folding and subsequent intermolecular aggregation driven by π–π stacking between azobenzene units and hydrogen bonding between amide groups (Figures S1a,d and S2). , By application of the exciton chirality rule, , 1R and 1S in their respective nanotoroids exhibit right-handed ( P ) and left-handed ( M ) pseudo-axial chirality (Figure S1c,f). Henceforth, these single-handed nanotoroids formed from either 1R or 1S will be denoted as “enantiopure P - or M -nanotoroids”, respectively.…”

Section: Resultsmentioning

confidence: 99%

Amplification of Molecular Asymmetry during the Hierarchical Self-Assembly of Foldable Azobenzene Dyads into Nanotoroids and Nanotubes

2022

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The amplification of molecular asymmetry through self-assembly is a phenomenon that not only comprehends the origin of homochirality in nature but also produces chiroptically active functional materials from molecules with minimal enantiomeric purity. Understanding how molecular asymmetry can be transferred and amplified into higher-order structures in a hierarchical selfassembly system is important but still unexplored. Herein, we present an intriguing example of the amplification of molecular asymmetry in hierarchically self-assembled nanotubes that feature discrete and isolatable toroidal intermediates. The hierarchical self-assembly is initiated via asymmetric intramolecular folding of scissor-shaped azobenzene dyads furnished with chiral side chains. When scalemic mixtures of the enantiomers are dissolved in a non-polar solvent and cooled to 20 °C, single-handed nanotoroids are formed, as confirmed using atomic force microscopy and circular dichroism analyses. A strong majority-rules effect at the nanotoroid level is observed and can be explained by a low mismatch penalty and a high helix-reversal penalty. The single-handed nanotoroids stack upon cooling to 0 °C to exclusively afford their respective single-handed nanotubes. Thus, the same degree of amplification of molecular asymmetry is realized at the nanotube level. The internal packing efficiency of molecules within nanotubes prepared from the pure enantiomers or their scalemic mixtures is likely different, as suggested by the absence of higher-order structure (supercoil) formation in the latter. Xray diffraction analysis of the anisotropically oriented nanotube films revealed looser molecular packing within the scalemic nanotubes, which clearly reflects the lower enantiomeric purity of their internal chiral side chains.

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“…However, many chiral compounds do not display distinct circular dichroism spectra and require the utilization of chromophoric reporters that are designed to bind the target molecule and to generate chiroptical signals suitable for stereochemical identification or quantification of the enantiomeric composition. The practicality of this approach for absolute configuration determination has been verified numerous times, especially by Nakanishi, Berova, Canary, Gawronski, Rosini and Borhan who have introduced an impressive suite of probes, including zinc‐porphyrin tweezers, that allow rational interpretation of the induced Cotton effects obtained upon covalent substrate binding or metal coordination, Figure 1 [12–33] . Because the sign of the generated CD curves is causally linked to the chirality of the analyte it reveals its absolute configuration.…”

Section: Introductionmentioning

confidence: 93%

Circular Dichroism Sensing: Strategies and Applications

Formen,

Howard,

Anslyn

et al. 2024

Angewandte Chemie

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The analysis of the absolute configuration, enantiomeric composition, and concentration of chiral compounds are frequently encountered tasks across the chemical and health sciences. Chiroptical sensing methods can streamline this work and allow high‐throughput screening with remarkable reduction of operational time and cost. During the last few years, significant methodological advances with innovative chirality sensing systems, the use of computer‐generated calibration curves, machine learning assistance, and chemometric data processing, to name a few, have emerged and are now matched with commercially available multi‐well plate CD readers. These developments have reframed the chirality sensing space and provide new opportunities that are of interest to a large group of chemists. This review will discuss chirality sensing strategies and applications with representative small‐molecule CD sensors. Emphasis will be given to important milestones and recent advances that accelerate chiral compound analysis by outperforming traditional methods, conquer new directions, and pioneering efforts that lie at the forefront of chiroptical high‐throughput screening developments. The goal is to provide the reader with a thorough understanding of the current state and a perspective of future directions of this rapidly emerging field.

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Point-to-Axial Chirality Transmission: A Highly Sensitive Triaryl Chirality Probe for Stereochemical Assignments of Amines

Cited by 5 publications

References 80 publications

“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

Amplification of Molecular Asymmetry during the Hierarchical Self-Assembly of Foldable Azobenzene Dyads into Nanotoroids and Nanotubes

Circular Dichroism Sensing: Strategies and Applications

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