Recent applications of chiral calixarenes in asymmetric catalysis

Durmaz, Mustafa; Halay, Erkan; Bozkurt, Selahattin

doi:10.3762/bjoc.14.117

Cited by 42 publications

(27 citation statements)

References 72 publications

(50 reference statements)

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“…Such unique properties of CD-MOFs, coupled with the innate chirality of γ-CD, allow substrates to be packed in highly orientationally and asymmetrically nanoconfined spaces. Although macrocyclic receptors, such as cyclodextrins, cucurbiturils, calixarenes, cavitands, and pillararenes, have all been explored extensively for their abilities to promote selectivities in chemical reactions, rarely have secondary coordination elements, such as metal cations, been introduced into these nanoconfined receptors to facilitate substrate pre-organization in a well-defined manner.…”

Section: Introductionmentioning

confidence: 99%

Selective Photodimerization in a Cyclodextrin Metal–Organic Framework

Chen

Đorđević

et al. 2021

J. Am. Chem. Soc.

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For the most part, enzymes contain one active site wherein they catalyze in a serial manner chemical reactions between substrates both efficiently and rapidly. Imagine if a situation could be created within a chiral porous crystal containing trillions of active sites where substrates can reside in vast numbers before being converted in parallel into products. Here, we report how it is possible to incorporate 1-anthracenecarboxylate (1-AC − ) as a substrate into a γ-cyclodextrincontaining metal−organic framework (CD-MOF-1), where the metals are K + cations, prior to carrying out [4+4] photodimerizations between pairs of substrate molecules, affording selectively one of four possible regioisomers. One of the highyielding regioisomers exhibits optical activity as a result of the presence of an 8:1 ratio of the two enantiomers following separation by high-performance liquid chromatography. The solid-state superstructure of 1-anthracenecarboxylate potassium salt (1-ACK), which is co-crystallized with γ-cyclodextrin, reveals that pairs of substrate molecules are not only packed inside tunnels between spherical cavities present in CD-MOF-1, but also stabilizedin addition to hydrogen-bonding to the C-2 and C-3 hydroxyl groups on the D-glucopyranosyl residues present in the γ-cyclodextrin toriby combinations of hydrophobic and electrostatic interactions between the carboxyl groups in 1-AC − and four K + cations on the waistline between the two γ-cyclodextrin tori in the tunnels. These non-covalent bonding interactions result in preferred coconformations that account for the highly regio-and enantioselective [4+4] cycloaddition during photoirradiation. Theoretical calculations, in conjunction with crystallography, support the regio-and stereochemical outcome of the photodimerization.

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Section: Introductionmentioning

confidence: 99%

Selective Photodimerization in a Cyclodextrin Metal–Organic Framework

Chen

Đorđević

et al. 2021

J. Am. Chem. Soc.

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“…These studies are meaningful supplements to heterocyclic compounds related to natural product synthesis, structural analysis, and biological activity research. Heterocyclic compounds not only have biological activity [ 41 , 42 ], but also make outstanding contributions in the field of catalytic reactions [ 43 ] and as natural product extractants [ 44 , 45 ]. In our previous work, SGP was hydrolyzed to obtain the glycan portion (SCT-Asn).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Four Pentacyclic Triterpene–Sialylglycopeptide Conjugates and Their Affinity Assays with Hemagglutinin

Luo

et al. 2021

Molecules

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Influenza outbreaks pose a serious threat to human health. Hemagglutinin (HA) is an important target for influenza virus entry inhibitors. In this study, we synthesized four pentacyclic triterpene conjugates with a sialylglycopeptide scaffold through the Cu(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC) and prepared affinity assays of these conjugates with two HAs, namely H1N1 (A/WSN/1933) and H5N1 (A/Hong Kong/483/97), respectively. With a dissociation constant (KD) of 6.89 μM, SCT-Asn-betulinic acid exhibited the strongest affinity with the H1N1 protein. Furthermore, with a KD value of 9.10 μM, SCT-Asn-oleanolic acid exhibited the strongest affinity with the H5N1 protein. The conjugates considerably enhanced antiviral activity, which indicates that pentacyclic triterpenes can be used as a ligand to improve the anti-influenza ability of the sialylglycopeptide molecule by acting on the HA protein.

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“…These nano‐environments provide specific orientation, stabilization of reactants/intermediates undergoing reactions, [2] and may serve as molecular protectors or blocking groups in selective chemical reactions [3] . Ample examples of catalysis have been demonstrated with various host molecules such as cyclodextrins, [4] calix[ n ]arenes, [5] cucurbit[ n ]urils, [6] cavitands, [7] and self‐assembled metal‐organic cages [8] . Furthermore, host molecules have been frequently employed to fabricate various supramolecular ensembles for special applications [9] .…”

Section: Introductionmentioning

confidence: 99%

“…rigid, capacious,h ydrophobic cavities and exposed functional groups), which have led to at remendous increase in their popularity.V arious PA homologues with different cavity sizes (n = 5-10) can be prepared in as ingle step from commercially available reagents, [15] although even larger (n = 11-15) homologues are known. [16] Of these,p illar [5]arenes (P5A) and pillar [6]arenes (P6A) are the most common and most efficiently synthesized, [17] and the phenolic rims of these rigid pillar-like symmetrical structures can be chemically modified to increase solubility in desired media. [18] The electron-rich hydrophobic cavities can accommodate various guests through different noncovalent interactions such as hydrogen bonding, the hydrophobic effect, electrostatic stabilization, van der Waals forces,a s well as CH-p and p-p interactions.…”

Section: Introductionmentioning

confidence: 99%

Role of Functionalized Pillararene Architectures in Supramolecular Catalysis

et al. 2020

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The many useful features possessed by pillararenes (PAs; e.g. rigid, capacious, and hydrophobic cavities, as well as exposed functional groups) have led to a tremendous increase in their popularity since their first discovery in 2008. In this Minireview, we emphasize the use of functionalized PAs and their assembled supramolecular materials in the field of catalysis. We aim to provide a fundamental understanding and mechanism of the role PAs play in catalytic process. The topics are subdivided into catalysis promoted by the PA rim/cavity, PA‐based nanomaterials, and PA‐based polymeric materials. To the best of our knowledge, this is the first overview on PA‐based catalysis. This Minireview not only summarizes the fabrications and applications of PAs in catalysis but also anticipates future research efforts in applying supramolecular hosts in catalysis.

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Recent applications of chiral calixarenes in asymmetric catalysis

Cited by 42 publications

References 72 publications

Selective Photodimerization in a Cyclodextrin Metal–Organic Framework

Selective Photodimerization in a Cyclodextrin Metal–Organic Framework

Synthesis of Four Pentacyclic Triterpene–Sialylglycopeptide Conjugates and Their Affinity Assays with Hemagglutinin

Role of Functionalized Pillararene Architectures in Supramolecular Catalysis

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