Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

An Inorganic Click Reaction for the Synthesis of Interlocked Molecules.

ABSTRACT: We describe the use of the cyaphide-azide 1,3-dipolar cycloaddition reaction for the synthesis of a new class of inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron-deficient bis-azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents of Au(IDipp)(CP) (IDipp=1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene) to afford interlocked molecules via an inorganic click reaction. These transformations proceed in good yields (ca. 65 %) and in the absence of a catalyst. The resulting organometallic rotaxanes are air- and moisture-stable and can be purified by column chromatography under aerobic conditions. The targeted rotaxanes were characterized by multi-element nuclear magnetic resonance (NMR) spectroscopy, mass-spectrometry, and single-crystal X-ray diffraction.

SUBMITTER: Mapp A

PROVIDER: S-EPMC10953421 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

An Inorganic Click Reaction for the Synthesis of Interlocked Molecules.

Mapp Alex A Wilmore Jamie T JT Beer Paul D PD Goicoechea Jose M JM

Angewandte Chemie (International ed. in English) 20230811 38

We describe the use of the cyaphide-azide 1,3-dipolar cycloaddition reaction for the synthesis of a new class of inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron-deficient bis-azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents of Au(IDipp)(CP) (IDipp=1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene) to afford interlocked molecules via an inorganic click reaction. These transformations proceed in good yields (ca. 65 ...[more]

PMID: 37449867

Similar Datasets

A Flexible Synthesis of 68Ga-Labeled Carbonic Anhydrase IX (CAIX)-Targeted Molecules via CBT/1,2-Aminothiol Click Reaction.

Project description:We herein describe a flexible synthesis of a small library of 68Ga-labeled CAIX-targeted molecules via an orthogonal 2-cyanobenzothiazole (CBT)/1,2-aminothiol click reaction. Three novel CBT-functionalized chelators (1⁻3) were successfully synthesized and labeled with the positron emitter gallium-68. Cross-ligation between the pre-labeled bifunctional chelators (BFCs) and the 1,2-aminothiol-acetazolamide derivatives (8 and 9) yielded six new 68Ga-labeled CAIX ligands with high radiochemical yields. The click reaction conditions were optimized to improve the reaction rate for applications with short half-life radionuclides. Overall, our methodology allows for a simple and efficient radiosynthetic route to produce a variety of 68Ga-labeled imaging agents for tumor hypoxia.

| S-EPMC6337199 | biostudies-literature

Chemical Waltz of Organic Molecules "On Water": Saline-Assisted Sustainable Regioselective Synthesis of Fluorogenic Heterobioconjugates via Click Reaction.

Project description:A new sustainable green protocol for obtaining highly fluorogenic heterobioconjugates by a well-known copper-mediated azide-alkyne cycloaddition click reaction of nonfluorescent 3-azidocoumarins/benzyl azides (2a-f) and terminal alkynes (1a-e) using aqueous NaCl as a cheap and nontoxic salting-out agent under ultrasonication at ambient temperature is described. The presence of aqueous NaCl significantly influences the reaction by disturbing the water kosmotropes and augments the hydrophobic interaction of water-insoluble reactants, thus making the reaction feasible in water at neutral pH. The "beauty" of the presented ecofriendly approach is further boosted up by recycling the aqueous filtrate of the reaction mixture without further addition of NaCl, CuSO4·5H2O, and Na ascorbate up to seven cycles, resulting in effectively low copper loading (100 ppm) with excellent turn-over number (4850) and turn-over frequency (88.18 min-1). A gram-scale synthesis was also successfully achieved with 92% yield, further elaborating the scope of this methodology.

| S-EPMC6648582 | biostudies-literature

Ring rotation of ferrocene in interlocked molecules in single crystals.

Project description:This work describes unique molecular motions of ferrocene-containing interlocked molecules observed by single-crystal X-ray crystallography. The rotational flexibility of ferrocene is achieved using combinations of ferrocene-tethered ammonium and 30-membered ring dibenzo-crown ether. By contrast, ferrocene was locked in the complex with an 18-membered ring dibenzo-crown ether and CH2Cl2. When the complex was heated at 358 K, CH2Cl2 was removed from the complex, which led to drastic structural changes, including a semieclipsed-to-disordered transition of ferrocene and flipping of the dibenzo-crown ether.

| S-EPMC8179491 | biostudies-literature

Fast and efficient synthesis of microporous polymer nanomembranes via light-induced click reaction.

Project description:Conjugated microporous polymers (CMPs) are materials of low density and high intrinsic porosity. This is due to the use of rigid building blocks consisting only of lightweight elements. These materials are usually stable up to temperatures of 400 °C and are chemically inert, since the networks are highly crosslinked via strong covalent bonds, making them ideal candidates for demanding applications in hostile environments. However, the high stability and chemical inertness pose problems in the processing of the CMP materials and their integration in functional devices. Especially the application of these materials for membrane separation has been limited due to their insoluble nature when synthesized as bulk material. To make full use of the beneficial properties of CMPs for membrane applications, their synthesis and functionalization on surfaces become increasingly important. In this respect, we recently introduced the solid liquid interfacial layer-by-layer (LbL) synthesis of CMP-nanomembranes via Cu catalyzed azide-alkyne cycloaddition (CuAAC). However, this process featured very long reaction times and limited scalability. Herein we present the synthesis of surface grown CMP thin films and nanomembranes via light induced thiol-yne click reaction. Using this reaction, we could greatly enhance the CMP nanomembrane synthesis and further broaden the variability of the LbL approach.

| S-EPMC5372710 | biostudies-literature

Synthesis of Nitrogen-Rich Polymers by Click Polymerization Reaction and Gas Sorption Property.

Project description:Microporous organic polymers (MOPs) are promising materials for gas sorption because of their intrinsic and permanent porosity, designable framework, and low density. The introduction of nitrogen-rich building block in MOPs will greatly enhance the gas sorption capacity. Here, we report the synthesis of MOPs from the 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine unit and aromatic azides linkers by click polymerization reaction. Fourier transform infrared (FTIR) and solid-state 13C CP-MAS (Cross Polarization-Magic Angle Spinning) NMR confirm the formation of the polymers. CMOP-1 and CMOP-2 exhibit microporous networks with a BET (Brunauer⁻Emmett⁻Teller) surface area of 431 m²·g-1 and 406 m²·g-1 and a narrow pore size distribution under 1.2 nm. Gas sorption isotherms including CO₂ and H₂ were measured. CMOP-1 stores a superior CO₂ level of 1.85 mmol·g-1 at 273 K/1.0 bar, and an H₂ uptake of up to 2.94 mmol·g-1 at 77 K/1.0 bar, while CMOP-2, with its smaller surface area, shows a lower CO₂ adsorption capacity of 1.64 mmol·g-1 and an H₂ uptake of 2.48 mmol·g-1. In addition, I₂ vapor adsorption was tested at 353 K. CMOP-1 shows a higher gravimetric load of 160 wt%. Despite the moderate surface area, the CMOPs display excellent sorption ability for CO₂ and I₂ due to the nitrogen-rich content in the polymers.

| S-EPMC6100294 | biostudies-literature

One-, two- and three-dimensional interlocked polymers based on hybrid inorganic-organic rotaxanes.

Project description:We report three new polymers, based on mechanically interlocked inorganic-organic rotaxanes. They are made in very mild conditions and involve pyrimidine head groups binding to copper(ii) linking units. A two-dimensional 6,3 net and a three-dimensional 10,3b net are found depending on the solvent used in the reaction.

| S-EPMC11348830 | biostudies-literature

AT-CuAAC Synthesis of Mechanically Interlocked Oligonucleotides.

Project description:We present a simple strategy for the synthesis of main chain oligonucleotide rotaxanes with precise control over the position of the macrocycle. The novel DNA-based rotaxanes were analyzed to assess the effect of the mechanical bond on their properties.

| S-EPMC8016193 | biostudies-literature

Dynamic covalent self-assembly of mechanically interlocked molecules solely made from peptides.

Project description:Mechanically interlocked molecules (MIMs), such as rotaxanes and catenanes, have captured the attention of chemists both from a synthetic perspective and because of their role as simple prototypes of molecular machines. Although examples exist in nature, most synthetic MIMs are made from artificial building blocks and assembled in organic solvents. The synthesis of MIMs from natural biomolecules remains highly challenging. Here, we report on a synthesis strategy for interlocked molecules solely made from peptides, that is, mechanically interlocked peptides (MIPs). Fully peptidic, cysteine-decorated building blocks were self-assembled in water to generate disulfide-bonded dynamic combinatorial libraries consisting of multiple different rotaxanes, catenanes and daisy chains as well as more exotic structures. Detailed NMR spectroscopy and mass spectrometry characterization of a [2]catenane comprising two peptide macrocycles revealed that this structure has rich conformational dynamics reminiscent of protein folding. Thus, MIPs can serve as a bridge between fully synthetic MIMs and those found in nature.

| S-EPMC8446321 | biostudies-literature

Facile Synthesis of Sulfur-Containing Functionalized Disiloxanes with Nonconventional Fluorescence by Thiol-Epoxy Click Reaction.

Project description:Herein, a series of novel sulfur-containing functionalized disiloxanes based on a low-cost and commercially available material, i.e., 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and various thiol compounds were prepared by thiol-epoxy click reaction. It was found that both lithium hydroxide (LiOH) and tetrabutylammonium fluoride (TBAF) have high catalytic activity after optimizing the reaction condition, and the reaction can be carried out with high yields, excellent regioselectivity, mild reaction condition, and good tolerance of functional groups. These compounds exhibit excellent nonconventional fluorescence due to the formation of coordination bonds between Si atoms and heteroatoms (e.g., S or N) and can emit blue fluorescence upon ultraviolet (UV) irradiation. These results demonstrate that the thiol-epoxy click reaction could promisingly act as an efficient organosilicon synthetic methodology to construct various organosilicon materials with novel structures and functionality, and thus their application scope will be significantly expanded.

| S-EPMC10177946 | biostudies-literature

Exploring the Capability of Mechanically Interlocked Molecules in Anion Recognition: A Computational Insight.

Project description:The present study elucidated the role of both hydrogen and halogen bonds, from an electronic structure perspective, in the anion recognition process by the [2]catenane (1) containing a moiety with hydrogen bond donors entangled with another macrocyclic halogen bond donor. Spherical and nonspherical anions have been employed. The roles of different σ-hole donors have also been considered. The structure of 1 was modified by incorporating other σ-hole donors, namely bromine, chlorine, fluorine, as well as -Te-CH3 as a chalcogen bond donor, leading to the modified [2]catenanes 2-5. Insights into anion recognition were gained by quantifying the contributions of not only the mechanical but also hydrogen and halogen/chalcogen bonds to anion recognition using the GKS-EDA energy partition scheme and homodesmostic reactions scheme. GKS-EDA reveals that the anions Cl- and TS- exhibit the most stabilizing interactions with the 1 binding pocket. The EDA results confirm that by changing from a stronger σ-hole donor (I) to a weaker σ-hole donor (F) will have a considerable impact on anion interaction, thereby demonstrating that the halogen bonds formed between the [2]catenane and the anion play a pivotal role.

| S-EPMC11758374 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data