Exploiting the Dimerization Characteristic of H2PO4– to Promote Its Selective Recognition by a Tetra-Amido Macrocycle DOI
Chenxi Wang,

Min Du,

Feiying Ruan

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

Creating a confined cavity that matches the size and binding site of substrate is prevalent strategy to achieve selective recognition specific anions. However, this not only requires sophisticated receptor design but also leads challenging synthesis. In contribution, by utilizing dimerization characteristic H2PO4-, we demonstrate H2PO4- can be achieved in DMSO synthetically simple tetra-amido macrocycle (1). By reaction condition optimization, yield final cyclization was improved. Through 1H NMR titration studies, exhibit sharp contrast affinity between other anions, as well exclusive from competitive environments containing various Job's plot, nonlinear fitting, single-crystal X-ray diffraction, computational study, variable temperature NMR, DOSY mechanism 1+H2PO4- extensively studied, including stoichiometry (1:2 host-guest), stability constant (β2 = 1.4 × 105 M-2), sites, possible structure, corresponding hydrodynamic radius (rH). Binding studies DCM 50% methanol/chloroform further support proposed mechanism. This study therefore explores new approach taking advantage self-assembly characteristics substrates.

Language: Английский

Cooperative Anion−π Catalysis with Chiral Molecular Cages toward Enantioselective Desymmetrization of Anhydrides DOI
Ming Yue, Na Luo, Xudong Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Exploiting novel noncovalent interactions for catalysis design represents a fascinating direction. For the flexible and relatively weak anion−π interactions, manipulation of two or more π-acidic surfaces cooperative activation is highly desirable. Here, we demonstrate strategy based on chiral molecular cages with V-shaped electron-deficient cavities synergic binding dicarbonyl electrophiles toward enantioselective desymmetrization transformation. The were readily synthesized by incorporation additional base sites in one step. efficiently catalyzed methanolytic series meso cyclic anhydrides nearly quantitative yields up to 94% ee. In contrast, non-cage analogues simple control catalysts showed sluggish conversion much lower enantioselectivity. Crystal structure, substrate studies, theoretical modeling consistently suggested essential role cage harnessing efficient excellent selectivity control.

Language: Английский

Citations

0
One-Pot Synthesis of Tridentate Bicyclocalixarene Cage Molecules DOI
Na Lin, Rongrong Xie,

Haoqing Jia

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

Efficient one-pot synthesis of tridentate bicyclocalixarenes was developed by condensing phloroglucinol with dechlorinated pyrimidine or triazine a yield up to 58%. These cage-like molecules adopt symmetric three-blade propeller structure different terminal function groups and arm spans ranging from 7.5 15.8 Å. Due the 1,3-alternate configuration intermediate heterocalixarenes, cage can be prepared only benzene rings as upper lower caps. They will an ideal scaffold for preparation ultrathin two-dimensional materials.

Language: Английский

Citations

0
Solvent-mediated subcomponent self-assembly of covalent metallacycles for hierarchical porous materials synthesis DOI Creative Commons
Zhiwei Li,

Anlian Huang,

Zhenguo Wang

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A solvent-mediated subcomponent self-assembly strategy was developed for synthesizing covalent metallacycles with different shapes.

Language: Английский

Citations

0
Revisiting the Origins of Reactivity and Selectivity in the Pd6L4-Cage-Catalyzed Diels–Alder Reactions: A Combined Computational and Experimental Study DOI

Hui-Mei Shan,

Lin Li, Qian Wang

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Supramolecular metal–organic cages (MOCs) have gained attention as versatile catalytic platforms due to their self-assembled architectures and well-defined cavities, which mimic enzyme active sites enable spatial confinement. This confinement modulates the reaction pathways enhances performance. Recent studies highlight potential in various organic transformations, but factors governing MOC-catalyzed reactions remain incompletely understood. work builds on prior computational of Diels–Alder catalyzed by palladium-based MOCs, showing that common view transition-state stabilization via π–π interactions is not valid. Instead, we find between substrate ligands destabilize transition state. Additionally, theoretical regioselectivity, validated experimentally, suggest encapsulation efficiency key determining selectivity. These findings provide new insights into mechanisms reactions.

Language: Английский

Citations

0
Nickel (II) Macrocyclic Complexes: Template Synthesis, Spectroscopic Investigations, Electrochemical Behavior, DFT Studies, and Biological Evaluation DOI
Manish Yadav,

Sarita Beniwal,

Gulshan Kumar

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(15)

Published: April 1, 2025

Abstract A novel series of tetraaza nickel (II) macrocyclic complexes was prepared via template condensation involving the ligand 2‐[4‐bromo‐2‐(2‐oxo‐1,2‐diphenyl‐ethylideneamino)‐phenylimino]‐1,2‐diphenyl‐ethanone (ML) and selected diamines, such as 4‐chloro 1,2‐phenylenediamine, 4‐bromo 1,2‐diaminotoluene, 4‐nitro 1,2‐diaminopropane, ethylenediamine, in presence NiCl 2 .6H O. The its resulting were characterized through elemental analysis, molecular weight determination, a range spectral techniques, including IR, electronic spectra, 1 H NMR, mass spectrometry, X‐ray powder diffraction, DFT‐assisted structural characterization. DFT (TDDFT/B3LYP/6–311g(d) method) analysis representative Ni(II) supports plausible structures proposed based on spectroscopic studies. These analyses suggest that each complex adopts six‐coordinated octahedral geometry. Their redox behavior examined detail using cyclic voltammetry (CV). Furthermore, new tested for their antimicrobial, antioxidant, antidiabetic, antituberculosis activities. Antimicrobial tests conducted against E. coli, B. subtilis, A. niger , P. chrysogenum synthesized compounds. antioxidant properties assessed DPPH assay showed [Ni(C 41 29 BrCl N 4 )] exhibited highest activity, with an IC 50 value 89.13 mg/mL. Additionally, antimycobacterial where 40 3 demonstrated significant effectiveness inhibiting growth Mycobacterium tuberculosis .

Language: Английский

Citations

0
Exploiting the Dimerization Characteristic of H2PO4– to Promote Its Selective Recognition by a Tetra-Amido Macrocycle DOI
Chenxi Wang,

Min Du,

Feiying Ruan

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

Creating a confined cavity that matches the size and binding site of substrate is prevalent strategy to achieve selective recognition specific anions. However, this not only requires sophisticated receptor design but also leads challenging synthesis. In contribution, by utilizing dimerization characteristic H2PO4-, we demonstrate H2PO4- can be achieved in DMSO synthetically simple tetra-amido macrocycle (1). By reaction condition optimization, yield final cyclization was improved. Through 1H NMR titration studies, exhibit sharp contrast affinity between other anions, as well exclusive from competitive environments containing various Job's plot, nonlinear fitting, single-crystal X-ray diffraction, computational study, variable temperature NMR, DOSY mechanism 1+H2PO4- extensively studied, including stoichiometry (1:2 host-guest), stability constant (β2 = 1.4 × 105 M-2), sites, possible structure, corresponding hydrodynamic radius (rH). Binding studies DCM 50% methanol/chloroform further support proposed mechanism. This study therefore explores new approach taking advantage self-assembly characteristics substrates.

Language: Английский

Citations

0