Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Water-soluble macrocycles synthesized via the weak-link approach.

ABSTRACT: We report a general, high-yielding method for the synthesis of water-soluble complexes, which is based upon the weak-link approach to supramolecular coordination chemistry. Specifically, we have utilized oligomeric ethylene glycol functional groups appended to the aryl groups of the diphenylphosphine moieties to achieve solubility. Small molecules or halide ions can be used to expand these complexes into larger, more flexible macrocyclic structures. The realization of this approach should allow for the preparation of allosteric biomimetic structures which can be used in aqueous media.

SUBMITTER: Wiester MJ

PROVIDER: S-EPMC2742207 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Water-soluble macrocycles synthesized via the weak-link approach.

Wiester Michael J MJ Mirkin Chad A CA

Inorganic chemistry 20090901 17

We report a general, high-yielding method for the synthesis of water-soluble complexes, which is based upon the weak-link approach to supramolecular coordination chemistry. Specifically, we have utilized oligomeric ethylene glycol functional groups appended to the aryl groups of the diphenylphosphine moieties to achieve solubility. Small molecules or halide ions can be used to expand these complexes into larger, more flexible macrocyclic structures. The realization of this approach should allow ...[more]

PMID: 19637852

Similar Datasets

Triple-Decker Complexes Formed via the Weak Link Approach.

Project description:Through the weak link approach and a halide-induced ligand rearrangement process, semi-open and condensed triple-decker complexes (TDCs) were prepared and fully characterized. These triple-decker structures with tailorable layers through choice of hemilabile ligand starting materials can be chemically opened and closed to expose the interior layer in a reversible fashion using small-molecule and elemental anion ligand substitution reactions.

| S-EPMC2593806 | biostudies-literature

Nanometer-scale water-soluble macrocycles from nanometer-sized amino acids.

Project description:This paper introduces the unnatural amino acids m-Abc(2K) and o-Abc(2K) as nanometer-sized building blocks for the creation of water-soluble macrocycles with well-defined shapes. m-Abc(2K) and o-Abc(2K) are homologues of the nanometer-sized amino acid Abc(2K), which we recently introduced for the synthesis of water-soluble molecular rods of precise length (J. Am. Chem. Soc. 2007, 129, 7272). Abc(2K) is linear (180 degrees), m-Abc(2K) creates a 120 degree angle, and o-Abc(2K) creates a 60 degree angle. m-Abc(2K) and o-Abc(2K) are derivatives of 3'-amino-(1,1'-biphenyl)-4-carboxylic acid and 2'-amino-(1,1'-biphenyl)-4-carboxylic acid, with two propyloxyammonium side chains for water solubility. m-Abc(2K) and o-Abc(2K) are prepared as Fmoc-protected derivatives Fmoc-m-Abc(2K(Boc))-OH (1a) and Fmoc-o-Abc(2K(Boc))-OH (1b). These derivatives can be used alone or in conjunction with Fmoc-Abc(2K(Boc))-OH (1c) as ordinary amino acids in Fmoc-based solid-phase peptide synthesis. Building blocks 1a-c were used to synthesize macrocyclic "triangles" 9a-c, "parallelograms" 10a,b, and hexagonal "rings" 11a-d. The macrocycles range from a trimer to a dodecamer, with ring sizes from 24 to 114 atoms, and are 1-4 nm in size. Molecular modeling studies suggest that all the macrocycles except 10b should have well-defined triangle, parallelogram, and ring shapes if all of the amide linkages are trans and the o-alkoxy substituents are intramolecularly hydrogen bonded to the amide NH groups. The macrocycles have good water solubility and are readily characterized by standard analytical techniques, such as RP-HPLC, ESI-MS, and NMR spectroscopy. (1)H and (13)C NMR studies suggest that the macrocycles adopt conformations with all trans-amide linkages in CD(3)OD, that the "triangles" and "parallelograms" maintain these conformations in D(2)O, and that the "rings" collapse to form conformations with cis-amide linkages in D(2)O.

| S-EPMC2837776 | biostudies-literature

Pyrene-Appended Fluorescent Tweezers Generated via the Weak-Link Approach and Their Halide Recognition Properties.

Project description:Through the Weak-Link Approach, fluorescent condensed and open Cu(I) tweezer complexes were prepared and characterized. These complexes exhibit fluorescence-sensitive binding properties for halide anions. The solid-state structure of a non-fluorescent Rh(I) tweezer analogue, determined by X-ray crystallography, shows that the counter anion, Cl(-), is trapped in between the two amide groups of the tweezer arms through hydrogen bonds. Although the tweezer binds Cl(-), the open complex also binds Cl(-), showing that the main role of the metal is to increase the local concentration of the pyrenyl amide moieties so that 2:1 binding can take place.

| S-EPMC3241529 | biostudies-literature

Aryl Amination Using Soluble Weak Base Enabled by a Water-Assisted Mechanism.

Project description:The amination of aryl halides has become one of the most commonly practiced C-N bond-forming reactions in pharmaceutical and laboratory syntheses. The widespread use of strong or poorly soluble inorganic bases for amine activation nevertheless complicates the compatibility of this important reaction class with sensitive substrates as well as applications in flow and automated synthesis, to name a few. We report a palladium-catalyzed C-N coupling using Et3N as a weak, soluble base, which allows a broad substrate scope that includes bromo- and chloro(hetero)arenes, primary anilines, secondary amines, and amide type nucleophiles together with tolerance for a range of base-sensitive functional groups. Mechanistic data have established a unique pathway for these reactions in which water serves multiple beneficial roles. In particular, ionization of a neutral catalytic intermediate via halide displacement by H2O generates, after proton loss, a coordinatively unsaturated Pd-OH species that can bind amine substrate triggering intramolecular N-H heterolysis. This water-assisted pathway operates efficiently with even weak terminal bases, such as Et3N. The use of a simple, commercially available ligand, PAd3, is key to this water-assisted mechanism by promoting coordinative unsaturation in catalytic intermediates responsible for the heterolytic activation of strong element-hydrogen bonds, which enables broad compatibility of carbon-heteroatom cross-coupling reactions with sensitive substrates and functionality.

| S-EPMC7690001 | biostudies-literature

A diversity-oriented synthesis approach to macrocycles via oxidative ring expansion.

Project description:Macrocycles are key structural elements in numerous bioactive small molecules and are attractive targets in the diversity-oriented synthesis of natural product-based libraries. However, efficient and systematic access to diverse collections of macrocycles has proven difficult using classical macrocyclization reactions. To address this problem, we have developed a concise, modular approach to the diversity-oriented synthesis of macrolactones and macrolactams involving oxidative cleavage of a bridging double bond in polycyclic enol ethers and enamines. These substrates are assembled in only four or five synthetic steps and undergo ring expansion to afford highly functionalized macrocycles bearing handles for further diversification. In contrast to macrocyclization reactions of corresponding seco acids, the ring expansion reactions are efficient and insensitive to ring size and stereochemistry, overcoming key limitations of conventional approaches to systematic macrocycle synthesis. Cheminformatic analysis indicates that these macrocycles access regions of chemical space that overlap with natural products, distinct from currently targeted synthetic drugs.

| S-EPMC3359144 | biostudies-literature

Water-soluble Fe(II)-H2O complex with a weak O-H bond transfers a hydrogen atom via an observable monomeric Fe(III)-OH.

Project description:Understanding the metal ion properties that favor O-H bond formation versus cleavage should facilitate the development of catalysts tailored to promote a specific reaction, e.g., C-H activation or H2O oxidation. The first step in H2O oxidation involves the endothermic cleavage of a strong O-H bond (BDFE = 122.7 kcal/mol), promoted by binding the H2O to a metal ion, and by coupling electron transfer to proton transfer (PCET). This study focuses on details regarding how a metal ion's electronic structure and ligand environment can tune the energetics of M(HO-H) bond cleavage. The synthesis and characterization of an Fe(II)-H2O complex, 1, that undergoes PCET in H2O to afford a rare example of a monomeric Fe(III)-OH, 7, is described. High-spin 7 is also reproducibly generated via the addition of H2O to {[Fe(III)(O(Me2)N4(tren))]2-(?-O)}(2+) (8). The O-H bond BDFE of Fe(II)-H2O (1) (68.6 kcal/mol) is calculated using linear fits to its Pourbaix diagram and shown to be 54.1 kcal/mol less than that of H2O and 10.9 kcal/mol less than that of [Fe(II)(H2O)6](2+). The O-H bond of 1 is noticeably weaker than the majority of reported M(n+)(HxO-H) (M = Mn, Fe; n+ = 2+, 3+; x = 0, 1) complexes. Consistent with their relative BDFEs, Fe(II)-H2O (1) is found to donate a H atom to TEMPO(•), whereas the majority of previously reported M(n+)-O(H) complexes, including [Mn(III)(S(Me2)N4(tren))(OH)](+) (2), have been shown to abstract H atoms from TEMPOH. Factors responsible for the weaker O-H bond of 1, such as differences in the electron-donating properties of the ligand, metal ion Lewis acidity, and electronic structure, are discussed.

| S-EPMC4485620 | biostudies-literature

Water-soluble Pd nanoparticles synthesized from ω-carboxyl-S-alkanethiosulfate ligand precursors as unimolecular micelle catalysts.

Project description:This report describes a two-phase synthesis of water-soluble carboxylate-functionalized alkanethiolate-capped Pd nanoparticles from ω-carboxyl-S-alkanethiosulfate sodium salts. The two-phase methodology using the thiosulfate ligand passivation protocol allowed a highly specific control over the surface ligand coverage of these nanoparticles, which are lost in a one-phase aqueous system because of the base-catalyzed hydrolysis of thiosulfate to thiolate. Systematic synthetic variations investigated in this study included the concentration of ω-carboxyl-S-alkanethiosulfate ligand precursors and reducing agent, NaBH4, and the overall ligand chain length. The resulting water-soluble Pd nanoparticles were isolated and characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), (1)H NMR, UV-vis, and FT-IR spectroscopy. Among different variations, a decrease in the molar equivalent of NaBH4 resulted in a reduction in the surface ligand density while maintaining a similar particle core size. Additionally, reducing the chain length of the thiosulfate ligand precursor also led to the formation of stable nanoparticles with a lower surface coverage. Since the metal core size of these Pd nanoparticle variations remained quite consistent, direct correlation studies between ligand properties and catalytic activities against hydrogenation/isomerization of allyl alcohol could be performed. Briefly, Pd nanoparticles dissolved in water favored the hydrogenation of allyl alcohol to 1-propanol whereas Pd nanoparticles heterogeneously dispersed in chloroform exhibited a rather high selectivity towards the isomerization product (propanal). The results suggested that the surrounding ligand environments, such as the ligand structure, conformation, and surface coverage, were crucial in determining the overall activity and selectivity of the Pd nanoparticle catalysts.

| S-EPMC4072038 | biostudies-literature

Dispersing and Retarding Properties of Water-Soluble Tetrasulfonate Resorcin[4]arene and Pyrogallol[4]arene Macrocycles in Cement-Based Mortar.

Project description:Water-soluble tetrasulfonate resorcin[4]arene (1a and 1c) and pyrogallol[4]arene (1b) macrocycles were synthesized and investigated for their dispersing properties in cement-based mortars. Mortar tests clearly show that these polyhydroxylated macrocycles (nonpolymeric) work as cement dispersants. Setting time determinations indicate that the macrocycles 1a and 1b show a retarding effect that is reminiscent of the behavior of superplasticizers (SPs) functionalized with polyhydroxylated β-CDs. Finally, the addition of sulfate anions to the cement paste does not affect the dispersing abilities of 1b, probably due to the sulfate anion capture by H-bonding interactions with its OH groups at the upper rim.

| S-EPMC7391848 | biostudies-literature

Water-Soluble Polymer

Project description:Water-Soluble Polymer Raw sequence reads

| PRJNA1039989 | ENA

Size-control in the synthesis of oxo-bridged phosphazane macrocycles via a modular addition approach.

Project description:Inorganic macrocycles remain largely underdeveloped compared with their organic counterparts due to the challenges involved in their synthesis. Among them, cyclodiphosphazane macrocycles have shown to be promising candidates for supramolecular chemistry applications due to their ability to encapsulate small molecules or ions within their cavities. However, further developments have been handicapped by the lack of synthetic routes to high-order cyclodiphosphazane macrocycles. Moreover, current approaches allow little control over the size of the macrocycles formed. Here we report the synthesis of high-order oxygen-bridged phosphazane macrocycles via a "3 + n cyclisation" (n = 1 and 3). Using this method, an all-PIII high-order hexameric cyclodiphosphazane macrocycle was isolated, displaying a larger macrocyclic cavity than comparable organic crown-ethers. Our approach demonstrates that increasing building block complexity enables precise control over macrocycle size, which will not only generate future developments in both the phosphazane and main group chemistry but also in the fields of supramolecular chemistry.

| S-EPMC9814222 | 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