Browse
Submit Data
Databases
API
Help

Dataset Information

23 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions.

ABSTRACT: We have designed the first chiral diene-based metal-organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(i) complexes to afford highly active and enantioselective single-site solid catalysts for C-C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to ?,?-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

SUBMITTER: Sawano T

PROVIDER: S-EPMC5951194 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions.

Sawano Takahiro T Ji Pengfei P McIsaac Alexandra R AR Lin Zekai Z Abney Carter W CW Lin Wenbin W

Chemical science 20150914 12

We have designed the first chiral diene-based metal-organic framework (MOF), E2-MOF, and postsynthetically metalated E2-MOF with Rh(i) complexes to afford highly active and enantioselective single-site solid catalysts for C-C bond formation reactions. Treatment of E2-MOF with [RhCl(C2H4)2]2 led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E ...[more]

PMID: 29861953

Similar Datasets

Coordination-bond-directed synthesis of hydrogen-bonded organic frameworks from metal-organic frameworks as templates.

Project description:Controlled synthesis of hydrogen-bonded organic frameworks (HOFs) remains challenging, because the self-assembly of ligands is not only directed by weak hydrogen bonds, but also affected by other competing van der Waals forces. Herein, we demonstrate the coordination-bond-directed synthesis of HOFs using a preformed metal-organic framework (MOF) as the template. A MOF (CuI-TTFTB) based on two-coordinated CuI centers and tetrathiafulvalene-tetrabenzoate (TTFTB) ligands was initially synthesized. CuI-TTFTB was subsequently oxidized to the intermediate (CuII-TTFTB) and hydrated to the HOF product (TTFTB-HOF). Single-crystal-to-single-crystal (SC-SC) transformation was realized throughout the MOF-to-HOF transformation so that the evolution of structures was directly observed by single-crystal X-ray diffraction. The oxidation and hydration of the CuI center are critical to breaking the Cu-carboxylate bonds, while the synergic corbelled S⋯S and π⋯π interactions in the framework ensured stability of materials during post-synthetic modification. This work not only provided a strategy to guide the design and discovery of new HOFs, but also linked the research of MOFs and HOFs.

| S-EPMC8565389 | biostudies-literature

Monolithic metal-organic frameworks for carbon dioxide separation.

Project description:Carbon dioxide (CO2) is both a primary contributor to global warming and a major industrial impurity. Traditional approaches to carbon capture involve corrosive and energy-intensive processes such as liquid amine absorption. Although adsorptive separation has long been a promising alternative to traditional processes, up to this point there has been a lack of appropriate adsorbents capable of capturing CO2 whilst maintaining low regeneration energies. In the context of CO2 capture, metal-organic frameworks (MOFs) have gained much attention in the past two decades as potential materials. Their tuneable nature allows for precise control over the pore size and chemistry, which allows for the tailoring of their properties for the selective adsorption of CO2. While many candidate materials exist, the amount of research into material shaping for use in industrial processes has been limited. Traditional shaping strategies such as pelletisation involve the use of binders and/or mechanical processes, which can have a detrimental impact on the adsorption properties of the resulting materials or can result in low-density structures with low volumetric adsorption capacities. Herein, we demonstrate the use of a series of monolithic MOFs (monoUiO-66, monoUiO-66-NH2 & monoHKUST-1) for use in gas separation processes.

| S-EPMC8517963 | biostudies-literature

Highly Boosting Circularly Polarized Luminescence of Chiral Metal-Imidazolate Frameworks.

Project description:To develop a simple and general method for improving the circularly polarized luminescence (CPL) performances of materials is of great significance. In this work, two pairs of CPL-active homochiral metal-organic frameworks (MOFs) P/M-Et and P/M-Et(Cd) with eta topology are reported. In comparison to the reported isomorphic Zn-imidazolate MOFs P-Me and M-Me, both luminescence dissymmetry factor (glum ) and photoluminescence quantum yields (ΦPL ) of P-Et and M-Et are largely improved by simply changing the methyl group to an ethyl group of ligands in P-Et and M-Et. Furthermore, the |glum | values are significantly amplified up to 0.015 from 0.0057 by introducing the non-luminescent halogenated aromatics, while an enhanced fluorescence efficiency is observed simultaneously (from 27.2% to 47.3%). The figure of merit value is about 40 times larger than that of P-Me and M-Me. Similarly, the CPL performances of P/M-Et(Cd) are improved by about five times after encapsulating fluorobenzene molecules. This work represents a new and simple method for developing CPL-active MOF materials.

| S-EPMC10265085 | biostudies-literature

Highly ordered macroporous dual-element-doped carbon from metal-organic frameworks for catalyzing oxygen reduction.

Project description:Multiple heteroatom-doped carbons with 3D ordered macro/meso-microporous structures have not been realized by simple carbonization of metal-organic frameworks (MOFs). Herein, ordered macroporous phosphorus- and nitrogen-doped carbon (M-PNC) is prepared successfully by carbonization of double-solvent-induced MOF/polystyrene sphere (PS) precursors accompanied with spontaneous removal of the PS template, followed by post-doping. M-PNC shows a high specific surface area of 837 m2 g-1, nitrogen doping of 3.17 at%, and phosphorus doping of 1.12 at%. Thanks to the hierarchical structure, high specific surface area, and multiple heteroatom-doping, M-PNC exhibits unusual catalytic activity as an electrocatalyst for the oxygen reduction reaction. Computational calculation reveals that the P[double bond, length as m-dash]O group helps stabilize the adsorption of intermediates, and the position of P[double bond, length as m-dash]O relative to graphitic N significantly improves the activity of the adjacent carbons for electrocatalysis.

| S-EPMC8162149 | biostudies-literature

Simple chiral diene ligands provide high enantioselectivities in transition-metal-catalyzed conjugate addition reactions.

Project description:Chiral dienes possessing the bicyclo[2.2.2]octadiene framework were prepared readily through the [4 + 2] cycloaddition of ( R)-alpha-phellandrene with methyl propiolate as the key step. Diene 9, substituted with a tertiary alcohol on one of the two double bonds, is prepared in just one step from the cycloadduct and is highly effective as a chiral ligand for rhodium-catalyzed asymmetric conjugate addition reactions, giving the corresponding addition products with higher enantioselectivity than other chiral dienes.

| S-EPMC2666791 | biostudies-literature

Tunable chiral metal organic frameworks toward visible light-driven asymmetric catalysis.

Project description:A simple and effective strategy is developed to realize visible light-driven heterogeneous asymmetric catalysis. A chiral organic molecule, which only has very weak catalytic activity in asymmetric α-alkylation of aldehydes under visible light, is utilized as the ligand to coordinate with different types of metal ions, including Zn2+, Zr4+, and Ti4+, for construction of crystalline metal organic frameworks (MOFs). Impressively, when used as heterogeneous catalysts, all of the synthesized MOFs exhibit markedly enhanced activity. Furthermore, the asymmetric catalytic performance of these MOFs could be easily altered by selecting different metal ions, owing to the tunable electron transfer property between metal ions and chiral ligands. This work will provide a new approach for fabrication of heterogeneous catalysts and trigger more enthusiasm to conduct the asymmetric catalysis driven by visible light.

| S-EPMC5562422 | biostudies-other

Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal-Organic Framework.

Project description:Chiral metal-organic frameworks have attracted interest for enantioselective separations and catalysis because of their high crystallinity and pores with tunable shapes, sizes, and chemical environments. Chiral frameworks of the type M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) seem particularly promising for potential applications because of their excellent stability, high internal surface areas, and strongly polarizing open metal coordination sites within the channels, but to date these materials have been isolated only in racemic form. Here, we demonstrate that when appended with the chiral diamine trans-1,2-diaminocyclohexane (dach), Mg2(dobpdc) adsorbs carbon dioxide cooperatively to form ammonium carbamate chains, and the thermodynamics of CO2 capture are strongly influenced by enantioselective interactions within the chiral pores of the framework. We further show that it is possible to access both enantiomers of Mg2(dobpdc) with high enantiopurity (≥90%) via framework synthesis in the presence of varying quantities of d-panthenol, an inexpensive chiral induction agent. Investigation of dach-M2(dobpdc) samples following CO2 adsorption-using single-crystal and powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory calculations-revealed that the ammonium carbamate chains interact extensively with each other and with the chiral M2(dobpdc) pore walls. Subtle differences in the non-covalent interactions accessible in each diastereomeric phase dramatically impact the thermodynamics of CO2 adsorption.

| S-EPMC8230736 | biostudies-literature

Highly Efficient Bifunctional Amide Functionalized Zn and Cd Metal Organic Frameworks for One-Pot Cascade Deacetalization-Knoevenagel Reactions.

Project description:A pyridine-based amide functionalized tetracarboxylic acid, 5,5'-(pyridine-2, 6-dicarbonyl)bis(azanediyl)}diisophthalic acid (H4L), was synthesized and its coordination chemistry toward zinc(II) and cadmium(II) ions was studied. The reactions of H4L with Zn(NO3)2.6H2O and Cd(NO3)2.4H2O led to its full or partial deprotonation, respectively, and the formation of the 2D coordination polymers [Zn2(L)(H2O)4]n.4n(H2O) (1) and [Cd3(HL)2(DMF)4]n.4n(DMF) (2) (DMF = N,N'-dimethylformamide), respectively. They were characterized by elemental analysis, FT-IR, photoluminescence, thermogravimetry, and single-crystal and powder X-ray diffraction. In 1, the L4- ligand is planar with every carboxylate anion binding a Zn(II) cation and giving rise to a 2D grid with the metals with tetrahedral environments. In 2, the combination of bridging HL3- and dimethylformamide to form trinuclear Cd(II) clusters engenders secondary building block units and generates a layer-type 2D network with the metals with octahedral and pentagonal bipyramid coordination geometries. The topological analyses of 1 and 2 reveal 2,4-connected and 3,6-connected binodal nets, respectively. On account of the presence of Lewis acid (Zn or Cd centers) as well as basic (uncoordinated pyridine and amide groups) sites, 1 and (to a much lower extent) 2 effectively catalyze the one-pot cascade deacetalization-Knoevenagel condensation reactions under quite mild conditions. They act as heterogeneous catalysts, being easy to recover and recycle without losing activity.

| S-EPMC6824099 | biostudies-literature

Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions.

Project description:Porphyrin-based Metal-Organic Frameworks (Por-MOFs) constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

| S-EPMC6273352 | biostudies-literature

Metal-Organic Frameworks as Versatile Heterogeneous Solid Catalysts for Henry Reactions.

Project description:Metal-organic frameworks (MOFs) have become one of the versatile solid materials used for a wide range of applications, such as gas storage, gas separation, proton conductivity, sensors and catalysis. Among these fields, one of the more well-studied areas is the use of MOFs as heterogeneous catalysts for a broad range of organic reactions. In the present review, the employment of MOFs as solid catalysts for the Henry reaction is discussed, and the available literature data from the last decade are grouped. The review is organized with a brief introduction of the importance of Henry reactions and structural properties of MOFs that are suitable for catalysis. The second part of the review discusses the use of MOFs as solid catalysts for the Henry reaction involving metal nodes as active sites, while the third section provides data utilizing basic sites (primary amine, secondary amine, amides and urea-donating sites). While commenting on the catalytic results in these two sections, the advantage of MOFs over other solid catalysts is compared in terms of activity by providing turnover number (TON) values and the structural stability of MOFs during the course of the reaction. The final section provides our views on further directions in this field.

| S-EPMC7962073 | 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