Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

Щербакова, Э Г; Minami, Tsuyoshi; Brega, Valentina; James, Tony D.; Anzenbacher, Pavel

doi:10.1002/ange.201501736

Cited by 29 publications

(3 citation statements)

References 49 publications

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“…X‐ray crystal structures of 1 a (Figure S3), 1 d (Figure S4), 1 e (Figure S7) and 2 d (Figure S15) showed the iminoboronate structure with a dative bond between the imine nitrogen and tetrahedral boron centre [29] . The B−N dative bond lengths (1.662–1.684 Å) were similar to those in related iminoboronates [23a] and aminomethylboronate esters [20c] …”

Section: Resultssupporting

confidence: 69%

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac₅/rac₆ Ratio via the B−N and B−O Dynamic Covalent Bonds

et al. 2022

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Amidoboronates were prepared as a mixture of up to three isomers (rac 5 , meso 5 and rac 6 ) from the reductive coupling of N-aryl iminoboronates with either cobaltocene or decamethylcobaltocene in acetonitrile. The interconversion of rac 5 and rac 6 isomers via rearrangement of their dynamic covalent BÀ N bonds was investigated in solution by redissolving isolated crystals. The aniline para substituent and catechol within the amidoboronates tuned the rac 5 /rac 6 ratio; the rac 6 isomer predominated for amidoboronates based on pyrocatechol, ranging from a ratio of 0 : 1 with electron-withdrawing Cl substituents to 0.5 : 0.5 for electron-donating NMe 2 substituents. No interconversion was observed for the rac 5 isomers of amidoboronates based on tetrachlorocatechol. Furthermore, the rac 5 /rac 6 distribution was altered by catechol exchange of pyrocatechol for tetrachlorocatechol exploiting the dynamic covalent BÀ O bonds and the rac 5 isomer was the major isomer following exchange.

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Section: Resultssupporting

confidence: 69%

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac₅/rac₆ Ratio via the B−N and B−O Dynamic Covalent Bonds

et al. 2022

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“…Moreover, in the case of liquid membranes, there is a good chance for integrability with microplate platforms as the bases of generally applied high-throughput applications. However, assay-based enantioselective applications mainly focus on determining the enantiomeric composition [ 30 , 31 , 32 ], while assay-based enantioseparation still remains an unexploited area of separation science.…”

Section: Introductionmentioning

confidence: 99%

Enantiodiscriminating Lipophilic Liquid Membrane-Based Assay for High-Throughput Nanomolar Enantioenrichment of Chiral Building Blocks

et al. 2023

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The reported optical resolution method was designed to support high-throughput enantioseparation of molecular building blocks obtained by automated small-scale synthetic methods. Lipophilic esters of common resolving agents were prepared and used as liquid membranes on the indifferent polymer surface of a microtiter assay. Chiral model compounds were enriched in one of the enantiomers starting from the aqueous solutions of their racemic mixture. Enantiodiscrimination was provided by forming diastereomeric coordination complexes of lipophilic enantiopure esters with the enantiomers of the chiral building blocks inside the liquid membranes. This enantiomeric recognition resulted in a greater distribution ratio of the preferred isomer in the membrane phase, thus the process enables a simultaneous enantioenrichment of the solutions outside the membrane. This paper reports a novel microplate-integrated stereoselective membrane enrichment technique satisfying the need for automatable enantioseparation on a subpreparative scale.

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“…8,9 Molecularly imprinted polymers (MIPs) have more than 80 years of history, 10,11 considerable advances have been made on the fundamental study.…”

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confidence: 99%

Highly efficient electrochemical recognition and quantification of amine enantiomers based on a guest-free homochiral MOF

et al. 2017

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We facilely synthesized a novel guest-free homochiral metal-organic framework, (Cu 4 L 4 ) n [H 2 L ¼ N-(2-hydroxybenzyl)-L-leucine] in space group P1. The (Cu 4 L 4 ) n nanocrystals exhibit high electrochemical activity for rapidly discriminating chiral a-methylbenzylamine enantiomers and quantitatively determining the enantiomeric excess in the chiral amine mixture.Many important molecules in the modern pharmaceutical and agrochemical industries, are chiral-that is, they are not superimposable on their mirror image, the pair of asymmetric molecules are known as enantiomers. The recognition and quantication of enantiomers is a major challenge particularly owing to their identical physical and chemical properties in an achiral environment.1 In many cases, one of the enantiomers exhibits the desired responses while the other is inactive or even toxic.2-4 The present technology depends largely upon nuclear magnetic resonance (NMR), gas chromatography (GC) and high performance liquid chromatography (HPLC) based on homochiral stationary phases (CSPs), which is of particular importance for laboratories and industries in the discovery and development of enantiomeric substances and quality control of corresponding products.5-7 However, these methods require high concentrations of analytes, sophisticated operation, relatively expensive instrumentation, and GC and HPLC are also typically time-consuming. 8,9 Molecularly imprinted polymers (MIPs) have more than 80 years of history, 10,11 considerable advances have been made on the fundamental study. 12,13Although the approach behaves special desired selectivity because the MIPs create three-dimensional cross-linked polymers with tailor-made memory of the shape, size and functional groups for a template or target molecule, 14,15 this sometimes also suffers from some problems, such as incomplete template removal, poor mass transfer, low binding capacity and slow binding kinetics, which restricts its applications in various aspects.16 In contrast, the electrochemical sensors can provide highly selective, low cost, fast speed, real time and on-line operation. Unlike chromatographic instruments, the technology can be easily adapted for detecting a wide range and low concentrations of analytes, while remaining inexpensive. 17However, there are only a handful of progress at the present chiral sensing using this approach.The key of the electrochemical chiral sensing is the material used to prepare the sensor's electroactive surface. The emerging chiral metal-organic framework (CMOFs) are the intriguing class of crystalline materials formed usually by the selfassembly of metal ions and chiral polydentate ligands. These materials are highly promising for electrochemical chiral sensors owing to ultrahigh surface area, precise network structures, ne-tuned chiral channels and pores, regularly ordered functionalities and host-guest interactions involved.18,19 At present, however, only a few achiral MOFs have been attempted as electrochemical sensors for detecting a few achiral analyte...

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Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

Cited by 29 publications

References 49 publications

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac₅/rac₆ Ratio via the B−N and B−O Dynamic Covalent Bonds

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac₅/rac₆ Ratio via the B−N and B−O Dynamic Covalent Bonds

Enantiodiscriminating Lipophilic Liquid Membrane-Based Assay for High-Throughput Nanomolar Enantioenrichment of Chiral Building Blocks

Highly efficient electrochemical recognition and quantification of amine enantiomers based on a guest-free homochiral MOF

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Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

Cited by 29 publications

References 49 publications

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac5/rac6 Ratio via the B−N and B−O Dynamic Covalent Bonds

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac5/rac6 Ratio via the B−N and B−O Dynamic Covalent Bonds

Enantiodiscriminating Lipophilic Liquid Membrane-Based Assay for High-Throughput Nanomolar Enantioenrichment of Chiral Building Blocks

Highly efficient electrochemical recognition and quantification of amine enantiomers based on a guest-free homochiral MOF

Contact Info

Product

Resources

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The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac₅/rac₆ Ratio via the B−N and B−O Dynamic Covalent Bonds

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac₅/rac₆ Ratio via the B−N and B−O Dynamic Covalent Bonds