Amplification of chirality as a pathway to biological homochirality

Kawasaki, Tsuneomi; Soai, Kenso

doi:10.1016/j.jfluchem.2009.12.014

Cited by 37 publications

(22 citation statements)

References 106 publications

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“…Controlling the structure and conjugation length of the organic portion of metallopolymers is crucial to optimizing their electronic properties.P olymer length also determines the morphology of the material, impacting device performance,scalability of preparation, and solution processability, [15] which are essential considerations for bespoke device fabrication. [9a, 17] Similar helical polymeric motifs [18] are of biological relevance, [19] and are of interest in the field of foldamers, [1g, 20] polarized light emission, [21] and spintronics. [9a, 17] Similar helical polymeric motifs [18] are of biological relevance, [19] and are of interest in the field of foldamers, [1g, 20] polarized light emission, [21] and spintronics.…”

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confidence: 99%

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Self‐Assembly of Conjugated Metallopolymers with Tunable Length and Controlled Regiochemistry

et al. 2017

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Self-assembled materials can be designed to express useful optoelectronic properties; however, achieving structural control is a necessary precondition for the optimization of desired properties. Here we report a simple, metal-templated polymerization process that generates helical metallopolymer strands over 75 repeat units long (28 kDa) from a single bifunctional monomer and Cu . The resulting polymer consists of a double helix of two identical conjugated organic strands enclosing a central column of metal ions. The length of this metallopolymer can be controlled by adding monofunctional subcomponents to end-cap the conjugated ligands. The use of ditopic and bulky monotopic subcomponents, respectively, allows a head-to-head or head-to-tail double helix to be generated. Spectroscopic measurements of different polymer lengths demonstrate how control over polymer length leads to control over the electronic and luminescent properties of the resulting material, thereby enabling tunable white-light emission.

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“…Tw odistinct 19 FNMR spectral regions were identified, one of which was inferred to correspond to HH, and the other to HT,e nvironments ( Figure S16). Tw odistinct 19 FNMR spectral regions were identified, one of which was inferred to correspond to HH, and the other to HT,e nvironments ( Figure S16).…”

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Self‐Assembly of Conjugated Metallopolymers with Tunable Length and Controlled Regiochemistry

et al. 2017

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“…[97] Die Verstärkung von Isotopenchiralität [98] wurde zusammen mit asymmetrischer Autokatalyse als ein potenzieller Wegz ur biologischen Homochiralitätbeschrieben. [99] Auch wenn im Allgemeinen nicht erwartet wird, dass Isotopensubstitution eine Veränderung von Festkçrpereigenschaften mit sich bringt, wurden fürb estimmte Verbindungen nach Deuteriummarkierung isotopische Polymorphie einhergehend mit einer Veränderung der Kristallstruktur beschrieben. [100] Zudem kçnnen deuterierte Lçsungsmittel die molekulare Aggregation in Kristallisationsprozessen beeinflussen.…”

Section: Isotopeneffekte Bei Nicht-kovalenten Wechselwirkungenunclassified

Deuterium‐ und tritiummarkierte Verbindungen: Anwendungen in den modernen Biowissenschaften

Atzrodt¹,

Derdau²,

Kerr

et al. 2018

Angewandte Chemie

108

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Wasserstoffisotope sind einzigartige Werkzeuge zur Identifizierung und Erforschung biologischer oder chemischer Vorgänge. Wasserstoffisotopenmarkierungen erlauben den spurlosen und direkten Einbau einer zusätzlichen Masseneinheit oder eines radioaktiven Markers in ein organisches Molekül, und dies praktisch ohne Änderungen der chemischen Struktur, der physikalischen Eigenschaften oder der biologischen Aktivität. Die Verwendung von deuteriummarkierten Isotopologen zur Untersuchung der spezifischen massenspektrometrischen (MS) Muster, die von Gemischen biologisch relevanter Moleküle hervorgerufen werden, ermöglicht eine drastische Vereinfachung der Analyse. Solche Methoden ermöglichen nun tiefe Einblicke in einen großen, kontinuierlich anwachsenden Bereich von Anwendungen in den Biowissenschaften und darüber hinaus. Speziell Tritium (3H) wird zunehmend eingesetzt, insbesondere in der pharmazeutischen Wirkstoffsuche. Aufwand und Kosten der Synthese markierter Verbindungen werden durch die hohe Empfindlichkeit der Analyse und hohe Zuverlässigkeit der erhaltenen Daten mehr als ausgeglichen. In diesem Aufsatz werden Fortschritte bei der Verwendung von Wasserstoffisotopen in den Biowissenschaften beschrieben.

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“…[4] Amplification effects of the helicity in the polyisocianates [5a] and supramolecular polymers [5b] that results from hydrogen isotopes (D/H) have been reported. And discrimination of hydrogen isotope chirality using spectroscopic methods [6] and HPLC analyses with a chiral stationary phase [7] have been reported.Recently, we have reported asymmetric autocatalysis with amplification of ee values [8][9][10][11] that was triggered by chiral compounds resulting from hydrogen (D/H) [12] and carbon isotope ( 13 C/ 12 C) [13] substitutions. Meanwhile, the syntheses of chiral compounds resulting from oxygen isotope substitutions [14] and oxygen kinetic isotope effects (KIEs) [15] have been reported.…”

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confidence: 99%

“…Recently, we have reported asymmetric autocatalysis with amplification of ee values [8][9][10][11] that was triggered by chiral compounds resulting from hydrogen (D/H) [12] and carbon isotope ( 13 C/ 12 C) [13] substitutions. Meanwhile, the syntheses of chiral compounds resulting from oxygen isotope substitutions [14] and oxygen kinetic isotope effects (KIEs) [15] have been reported.…”

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Asymmetric Autocatalysis: Triggered by Chiral Isotopomer Arising from Oxygen Isotope Substitution

et al. 2011

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The substitution of the atoms in the enantiotopic moiety of an achiral molecule by their isotopes makes the present molecule chiral. [1, 2] Isotopically labeled compounds [3] have been used to elucidate structural information, [3b] mechanisms of organic reactions, [3c-e] and drug kinetics, [3f] however, asymmetric synthesis using the chirality generated by isotope substitution alone is difficult because of the very low enantiomeric excess (ee) displayed when using deuterated chiral compounds as a source of chirality. [4] Amplification effects of the helicity in the polyisocianates [5a] and supramolecular polymers [5b] that results from hydrogen isotopes (D/H) have been reported. And discrimination of hydrogen isotope chirality using spectroscopic methods [6] and HPLC analyses with a chiral stationary phase [7] have been reported.Recently, we have reported asymmetric autocatalysis with amplification of ee values [8][9][10][11] that was triggered by chiral compounds resulting from hydrogen (D/H) [12] and carbon isotope ( 13 C/ 12 C) [13] substitutions. Meanwhile, the syntheses of chiral compounds resulting from oxygen isotope substitutions [14] and oxygen kinetic isotope effects (KIEs) [15] have been reported. However, to the best of our knowledge, there have been no reports of asymmetric synthesis or induction utilizing chiral compounds resulting from oxygen isotope substitution. Therefore, asymmetric autocatalysis initiated by chiral compounds arising from 18 O/ 16 O substitution is challenging.We selected a meso compound as the oxygen isotope enantiomer (Scheme 1). Achiral meso hydrobenzoin forms chiral oxygen isotopomers 1 after 18 O labeling of the hydroxy group in an enantioselective manner. These diols should be chiral only as a result of the oxygen isotope ( 18 O/ 16 O) substitution. The enantiomer whose 18 O atom is bound to the S-configured carbon center is described as [ 18 O](S)-1, while the opposite is described as [ 18 O](R)-1.Herein we report the first asymmetric induction by chiral compounds arising from oxygen isotope substitution in conjunction with asymmetric autocatalysis (Scheme 1). The chiral compound created by oxygen isotope substitution serves as the chiral trigger of asymmetric autocatalysis to afford alkanol 3 with high ee values. The relationship between the absolute configurations of the chiral 18 O-labeled hydrobenzoin ([ 18 O]1) and the product alkanol 3 is reproducible.The enantiomers of [ 18 O]1 were synthesized from chiral trans-stilbene oxide (4), which was obtained by resolution of its racemate by HPLC methods using a chiral stationary phase. The enantiomers of oxide 4 had ee values greater than 99.5 % and were submitted to the epoxide-opening reaction using [ 18 O]H 2 O under basic reaction conditions (Figure 1 A). By using 2-methoxyethanol as a cosolvent, the hydrolysis of the epoxide by [ 18 O]H 2 O proceeded stereoselectively to form the chiral [ 18 O]1 predominantly. The enantioenrichment of the synthesized compound 1 was confirmed by 13 C NMR spectroscopic analysis...

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Amplification of chirality as a pathway to biological homochirality

Cited by 37 publications

References 106 publications

Self‐Assembly of Conjugated Metallopolymers with Tunable Length and Controlled Regiochemistry

Self‐Assembly of Conjugated Metallopolymers with Tunable Length and Controlled Regiochemistry

Deuterium‐ und tritiummarkierte Verbindungen: Anwendungen in den modernen Biowissenschaften

Asymmetric Autocatalysis: Triggered by Chiral Isotopomer Arising from Oxygen Isotope Substitution

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