“Unclosed Cryptands”: A Point of Departure for Developing Potent Neutral Anion Receptors

Dąbrowa, Kajetan; Pawlak, Marcin; Duszewski, Piotr; Jurczak, Janusz

doi:10.1021/ol303065k

Cited by 28 publications

(53 citation statements)

References 49 publications

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“…Unclosed cryptands Uc1-Uc5 [30][31][32] are structurally related to previously mentioned macrocycles M1-M13, however, only one side contains meso diacid moiety (dipicolinic acid), while the other side is constructed here from diacid derived from 2,6-dihydroxyaniline. The nitrogen atom of the latter group is a part of amide equipped with an additional p-nitrophenyl substituent (lariat arm) which is introduced at the intraannular position of the macroring.…”

Section: Unclosed Cryptands (Group Iii)mentioning

confidence: 99%

Catching the chloride: searching for non-Hofmeister selectivity behavior in systematically varied polyamide macrocyclic receptors

et al. 2017

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The binding selectivity of structurally simple anion receptors is governed by the Hofmeister series (SO > HPO > carboxylates ∼ HPO > HCO > Cl), and exceptions to this rule are rare and require utilization of structurally sophisticated receptors. In this paper we examined a set of 48 structurally diverse anion receptors, barely one fourth of which exhibit selectivity for chloride over more basic dihydrogen phosphate (HPO) or carboxylates (MeCO and PhCO). Searching for regularities in the properties of these mainly macrocyclic-derived receptors across quite systematic changes in structure, combined with analysis of multiple crystal structures, allowed us to identify the crucial structural features that are likely required for the occurrence of the phenomenon of selective chloride binding. Examination of a subset of other 'case study' receptors reported in the literature as being particularly chloride-selective served as a confirmation of our hypotheses. As such, our findings are valid for all artificial receptors with exceptional selectivity for chloride, as well as for natural chloride channel proteins (ClC).

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Section: Unclosed Cryptands (Group Iii)mentioning

confidence: 99%

Catching the chloride: searching for non-Hofmeister selectivity behavior in systematically varied polyamide macrocyclic receptors

et al. 2017

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“…There are several types of hydrogen‐bonding building blocks that contain (benzo)pyrrole, urea, and amide units . Owing to their relatively high anion affinity, bisamide building blocks constructed of aromatic skeletons are particularly attractive, as they are readily incorporated into more complex macrocyclic, cryptand, and polycyclic structures ,. Such receptors tend to have exceptionally high affinities for anions and are promising structures in selective anion binding.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Binding Site Geometry on Anion‐Binding Selectivity: A Case Study of Macrocyclic Receptors Built on the Azulene Skeleton

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Wasiłek

Dydio

et al. 2018

Chemistry A European J

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An understanding of host-guest noncovalent interactions lies at the very heart of supramolecular chemistry. Often a minute change to the structure of a host molecule's binding site can have a dramatic impact on a prospective host-guest binding event, changing the relative selectivity for potential guest molecules. With the overall goal of aiding the rational design of selective and effective receptors for anions, we have studied the influence of small perturbations in binding site geometry for a series of five closely related 20-membered macrocyclic tetra-amide receptors, constructed from two building blocks from a pool of azulene-5,7-bisamide, azulene-1,3-bisamide, and dipicolinic bisamide units. The solid-state structures revealed that the conformational preferences of the free receptors are driven by the inherent preferences of the building blocks, yet in some cases the macrocyclic topology is able to over-ride these to promote pre-organized conformations favorable for anion binding. The solid-state structures of the chloride complexes of these receptors revealed that although all the receptors can adapt to binding to the challenging small Cl guest with all the NH groups, only receptors containing azulene-5,7-bisamide units form short and linear, and therefore strong, hydrogen-bonding interactions. These conclusions are further supported by studies in solution. Although all the receptors showed high affinities toward a series of anions (H PO , PhCO , Cl , and Br ), even in a highly competitive polar medium (DMSO/25 % MeOH), only receptors containing azulene-5,7-bisamide units exhibited non-inherent selectivity for Cl over PhCO , breaking the Hofmeister trend of selectivity. The data presented herein highlight the privileged properties of the azulene-5,7-bisamide building block for binding to chloride anions and provide guidelines for the construction of selective and efficient anion receptors with prospective practical applications.

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“…It was, however, identified that achiral molecules, particularly macrocyclic structures, may occur as homochiral species in a crystalline form . In recent decades, we demonstrated array of cyclic systems, mainly based on a concept of unclosed cryptands (specific lariat molecules), with various pending arms that affect features of cyclic scaffolds . It turned out that some of these proved to be chiral in a solid state, upon crystallization from a solution.…”

Section: Introductionmentioning

confidence: 99%

“…decades, we demonstrated array of cyclic systems, mainly based on a concept of unclosed cryptands (specific lariat molecules), with various pending arms that affect features of cyclic scaffolds. [36][37][38][39][40][41] It turned out that some of these proved to be chiral in a solid state, upon crystallization from a solution. Secondly, crystals of macrocyclic imines with broken symmetry were recently obtained, exhibiting outstanding enantiomeric excess, with respect to the single crystal.…”

Section: Introductionmentioning

confidence: 99%

Chirality of 20‐membered unclosed cryptand: Macroring distortion via lariat arm modification

et al. 2017

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Some of 19‐membered unclosed cryptands were recognized as chiral species in a solid state. While, in terms of 20‐membered macrocycle, we tune the lariat arm, developing the synthesis of α‐ and β‐naphthyl terminated moieties to gain the structural control over chirality phenomena of these systems. Indirect synthetic approach delineates the way to reach both target structures. Solely, macrocycle functionalized with the β‐naphthyl group is capable of desirable interactions with the frame of entity inducing its stronger bending that leads to the chiral crystals formation. Their structural features were examined by single crystal X‐ray diffraction and chiroptical method, represented by ECD/UV spectroscopy.

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“Unclosed Cryptands”: A Point of Departure for Developing Potent Neutral Anion Receptors

Cited by 28 publications

References 49 publications

Catching the chloride: searching for non-Hofmeister selectivity behavior in systematically varied polyamide macrocyclic receptors

Catching the chloride: searching for non-Hofmeister selectivity behavior in systematically varied polyamide macrocyclic receptors

The Influence of Binding Site Geometry on Anion‐Binding Selectivity: A Case Study of Macrocyclic Receptors Built on the Azulene Skeleton

Chirality of 20‐membered unclosed cryptand: Macroring distortion via lariat arm modification

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