Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Evaluating continuous chirality measure as a 3D descriptor in chemoinformatics applied to asymmetric catalysis.

ABSTRACT: Continuous Chirality Measure (CCM) is a computational metric by which to quantify the chirality of a compound. In enantioselective catalysis, prior work has postulated that CCM is correlated to selectivity and can be used to understand which structural features dictate catalyst efficacy. Herein, the investigation of CCM as a metric capable of guiding catalyst optimization is explored. Conformer-dependent CCM is also explored. Finally, CCM is used with Sterimol parameters to significantly improve the performance of Random Forest models.

SUBMITTER: Zahrt AF

PROVIDER: S-EPMC6980240 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Evaluating continuous chirality measure as a 3D descriptor in chemoinformatics applied to asymmetric catalysis.

Zahrt Andrew F AF Denmark Scott E SE

Tetrahedron letters 20190206 13

Continuous Chirality Measure (CCM) is a computational metric by which to quantify the chirality of a compound. In enantioselective catalysis, prior work has postulated that CCM is correlated to selectivity and can be used to understand which structural features dictate catalyst efficacy. Herein, the investigation of CCM as a metric capable of guiding catalyst optimization is explored. Conformer-dependent CCM is also explored. Finally, CCM is used with Sterimol parameters to significantly improve ...[more]

PMID: 31983782

Similar Datasets

Chirality Transfer and Asymmetric Catalysis: Two Strategies toward the Enantioselective Formal Total Synthesis of (+)-Gelsenicine.

Project description:Two strategies are described en route to an enantioselective total synthesis of gelsenicine. One approach centers on a chirality transfer cycloisomerization that ultimately fell short. Separately, an asymmetric catalysis route utilizing bisphosphine-gold-catalyzed cycloisomerization was pursued. A catalytic system was identified that provided a synthetic intermediate in our Gelsemium alkaloid syntheses in high enantiopurity and with absolute configuration determined by electronic circular dichroism, thus representing an enantioselective formal total synthesis of (+)-gelsenicine.

| S-EPMC9297687 | biostudies-literature

Parametrization of Non-covalent Interactions for Transition State Interrogation Applied to Asymmetric Catalysis.

Project description:The use of computed interaction energies and distances as parameters in multivariate correlations is introduced for postulating non-covalent interactions. This new class of descriptors affords multivariate correlations for two diverse catalytic systems with unique non-covalent interactions at the heart of each process. The presented methodology is validated by directly connecting the non-covalent interactions defined through empirical data set analyses to the computationally derived transition states.

| S-EPMC5639935 | biostudies-literature

Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold.

Project description:Use of chiral solvents in asymmetric synthesis as a sole source of enantioselection remains largely unexplored in organic synthesis. We found that the use of a helical macromolecular catalyst of which helical chirality is dynamically formed in chiral solvents allowed several mechanistically different reactions to proceed with high enantioselectivity. In this system, the chirality of the solvent, such as limonene, induces a configurational imbalance to the helical macromolecular scaffold of the catalyst, and in turn to the reaction products through palladium-catalyzed asymmetric reactions including Suzuki-Miyaura cross-coupling (up to 98% ee), styrene hydrosilylation (up to 95% ee), and silaboration (up to 89% ee). Not only enantiomerically pure limonene but also limonene with low enantiomeric excesses induce single-handed helical structures with majority-rule-based amplification of homochirality. The helical conformation of the macromolecular catalyst was retained even in the absence of limonene in the solid state, enabling asymmetric cross-coupling in achiral solvent with high enantioselectivity.

| S-EPMC6661863 | biostudies-literature

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis.

Project description:The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal?organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

| S-EPMC5684417 | biostudies-other

Central-to-Folding Chirality Control: Asymmetric Synthesis of Multilayer 3D Targets With Electron-Deficient Bridges.

Project description:New multilayer 3D chiral molecules have been designed and synthesized asymmetrically through the strategy of center-to-multilayer folding chirality control and double Suzuki couplings. Individual diastereoisomers were readily obtained and separated via flash column chromatography. The key diastereoisomer was further converted into corresponding enantiomers. These enantiomers possess electron-deficient aromatic bridges layered with top and bottom aromatic scaffolds. X-ray structural analysis has unambiguously confirmed the configuration, and intermolecular packing results in regular planar patterns in solid crystals. The synthesis was achieved in a total of ten steps starting from commercially available starting materials.

| S-EPMC9010227 | biostudies-literature

Chirality transfer from a 3D macro shape to the molecular level by controlling asymmetric secondary flows.

Project description:Homochirality is a fundamental feature of living systems, and its origin is still an unsolved mystery. Previous investigations showed that external physical forces can bias a spontaneous symmetry breaking process towards deterministic enantioselection. But can the macroscopic shape of a reactor play a role in chiral symmetry breaking processes? Here we show an example of chirality transfer from the chiral shape of a 3D helical channel to the chirality of supramolecular aggregates, with the handedness of the helical channel dictating the direction of enantioselection in the assembly of an achiral molecule. By combining numerical simulations of fluid flow and mass transport with experimental data, we demonstrated that the chiral information is transferred top-down thanks to the interplay between the hydrodynamics of asymmetric secondary flows and the precise spatiotemporal control of reagent concentration fronts. This result shows the possibility of controlling enantioselectively molecular processes at the nanometer scale by modulating the geometry and the operating conditions of fluidic reactors.

| S-EPMC8976054 | biostudies-literature

Heterobifunctional Rotaxanes for Asymmetric Catalysis.

Project description:Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine-based thread and a chiral 1,1'-binaphthyl-phosphoric-acid-based macrocycle. High-level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non-interlocked counterparts in terms of reaction rates and stereoselectivities.

| S-EPMC7154720 | biostudies-literature

BCL::EMAS--enantioselective molecular asymmetry descriptor for 3D-QSAR.

Project description:Stereochemistry is an important determinant of a molecule's biological activity. Stereoisomers can have different degrees of efficacy or even opposing effects when interacting with a target protein. Stereochemistry is a molecular property difficult to represent in 2D-QSAR as it is an inherently three-dimensional phenomenon. A major drawback of most proposed descriptors for 3D-QSAR that encode stereochemistry is that they require a heuristic for defining all stereocenters and rank-ordering its substituents. Here we propose a novel 3D-QSAR descriptor termed Enantioselective Molecular ASymmetry (EMAS) that is capable of distinguishing between enantiomers in the absence of such heuristics. The descriptor aims to measure the deviation from an overall symmetric shape of the molecule. A radial-distribution function (RDF) determines a signed volume of tetrahedrons of all triplets of atoms and the molecule center. The descriptor can be enriched with atom-centric properties such as partial charge. This descriptor showed good predictability when tested with a dataset of thirty-one steroids commonly used to benchmark stereochemistry descriptors (r² = 0.89, q² = 0.78). Additionally, EMAS improved enrichment of 4.38 versus 3.94 without EMAS in a simulated virtual high-throughput screening (vHTS) for inhibitors and substrates of cytochrome P450 (PUBCHEM AID891).

| S-EPMC3805266 | biostudies-literature

Multilayer 3D Chirality and Its Synthetic Assembly.

Project description:3D chirality of sandwich type of organic molecules has been discovered. The key element of this chirality is characterized by three layers of structures that are arranged nearly in parallel fashion with one on top and one down from the center plane. Individual enantiomers of these molecules have been fully characterized by spectroscopies with their enantiomeric purity measured by chiral HPLC. The absolute configuration was unambiguously assigned by X-ray diffraction analysis. This is the first multilayer 3D chirality reported and is anticipated to lead to a new research area of asymmetric synthesis and catalysis and to have a broad impact on chemical, medicinal, and material sciences in future.

| S-EPMC6750085 | biostudies-literature

Dynamic control of chirality in phosphine ligands for enantioselective catalysis.

Project description:Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly achieved through ligand design with chiral bisphosphines being widely applied as privileged ligands. Switchable phosphine ligands, in which chirality is modulated through an external trigger signal, might offer attractive possibilities to change enantioselectivity in a catalytic process in a non-invasive manner avoiding renewed ligand synthesis. Here we demonstrate that a photoswitchable chiral bisphosphine based on a unidirectional light-driven molecular motor, can be used to invert the stereoselectivity of a palladium-catalysed asymmetric transformation. It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction.

| S-EPMC4389239 | 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