Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chiral Amplification of Phosphoramidates of Amines and Amino Acids in Water.

ABSTRACT: The origin of biomolecular homochirality continues to be one of the most fascinating aspects of prebiotic chemistry. Various amplification strategies for chiral compounds to enhance a small chiral preference have been reported, but none of these involves phosphorylation, one of nature's essential chemical reactions. Here we present a simple and robust concept of phosphorylation-based chiral amplification of amines and amino acids in water. By exploiting the difference in solubility of a racemic phosphoramidate and its enantiopure form, we achieved enantioenrichment in solution. Starting with near racemic, phenylethylamine-based phosphoramidates, ee's of up to 95 % are reached in a single amplification step. Particularly noteworthy is the enantioenrichment of phosphorylated amino acids and their derivatives, which might point to a potential role of phosphorus en-route to prebiotic homochirality.

SUBMITTER: Daskova V

PROVIDER: S-EPMC8252365 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chiral Amplification of Phosphoramidates of Amines and Amino Acids in Water.

Dašková Vanda V Buter Jeffrey J Schoonen Anne K AK Lutz Martin M de Vries Folkert F Feringa Ben L BL

Angewandte Chemie (International ed. in English) 20210406 20

The origin of biomolecular homochirality continues to be one of the most fascinating aspects of prebiotic chemistry. Various amplification strategies for chiral compounds to enhance a small chiral preference have been reported, but none of these involves phosphorylation, one of nature's essential chemical reactions. Here we present a simple and robust concept of phosphorylation-based chiral amplification of amines and amino acids in water. By exploiting the difference in solubility of a racemic ...[more]

PMID: 33605523

Similar Datasets

Analysis of amino acids, hydroxy acids, and amines in CR chondrites.

Project description:The abundances, relative distributions, and enantiomeric and isotopic compositions of amines, amino acids, and hydroxy acids in Miller Range (MIL) 090001 and MIL 090657 meteorites were determined. Chiral distributions and isotopic compositions confirmed that most of the compounds detected were indigenous to the meteorites and not the result of terrestrial contamination. Combined with data in the literature, suites of these compounds have now been analyzed in a set of six CR chondrites, spanning aqueous alteration types 2.0-2.8. Amino acid abundances ranged from 17 to 3300 nmol g-1 across the six CRs; hydroxy acid abundances ranged from 180 to 1800 nmol g-1; and amine abundances ranged from 40 to 2100 nmol g-1. For amino acids and amines, the weakly altered chondrites contained the highest abundances, whereas hydroxy acids were most abundant in the more altered CR2.0 chondrite. Because water contents in the meteorites are orders of magnitude greater than soluble organics, synthesis of hydroxy acids, which requires water, may be less affected by aqueous alteration than amines and amino acids that require nitrogen-bearing precursors. Two chiral amino acids that were plausibly extraterrestrial in origin were present with slight enantiomeric excesses: L-isovaline (~10% excess) and D-β-amino-n-butyric acid (~9% excess); further studies are needed to verify that the chiral excess in the latter compound is truly extraterrestrial in origin. The isotopic compositions of compounds reported here did not reveal definitive links between the different compound classes such as common synthetic precursors, but will provide a framework for further future in-depth analyses.

| S-EPMC7839561 | biostudies-literature

Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate.

Project description:Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a 'right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas 'left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a 'mother' subunit nanoparticle spawns a slightly tilted, consequential 'daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures.

| S-EPMC5399303 | biostudies-literature

Photoredox α-vinylation of α-amino acids and N-aryl amines.

Project description:A new coupling protocol has been developed that allows the union of vinyl sulfones with photoredox-generated α-amino radicals to provide allylic amines of broad diversity. Direct C-H vinylations of N-aryl tertiary amines, as well as decarboxylative vinylations of N-Boc α-amino acids, proceed in high yield and with excellent olefin geometry control. The utility of this new allyl amine forming reaction has been demonstrated via the syntheses of several natural products and a number of established pharmacophores.

| S-EPMC4140496 | biostudies-literature

Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters.

Project description:The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral β-ketosulfones, and the reductive elimination of related α-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of α-amino aldehydes.

| S-EPMC6273449 | biostudies-literature

Breakdown of chiral recognition of amino acids in reduced dimensions.

Project description:The homochirality of amino acids in living organisms is one of the great mysteries in the phenomena of life. To understand the chiral recognition of amino acids, we have used scanning tunnelling microscopy to investigate the self-assembly of molecules of the amino acid tryptophan (Trp) on Au(111). Earlier experiments showed only homochiral configurations in the self-assembly of amino acids, despite using a mixture of the two opposite enantiomers. In our study, we demonstrate that heterochiral configurations can be favored energetically when L- and D-Trp molecules are mixed to form self-assembly on the Au surface. Using density functional theory calculations, we show that the indole side chain strongly interacts with the Au surface, which reduces the system effectively to two-dimension, with chiral recognition disabled. Our study provides important insight into the recognition of the chirality of amino acid molecules in life.

| S-EPMC7527561 | biostudies-literature

Visible-light photoredox synthesis of unnatural chiral α-amino acids.

Project description:Unnatural chiral α-amino acids are widely used in fields of organic chemistry, biochemistry and medicinal chemistry, and their synthesis has attracted extensive attention. Although the asymmetric synthesis provides some efficient protocols, noble and elaborate catalysts, ligands and additives are usually required which leads to high cost. Distinctly, it is attractive to make unnatural chiral α-amino acids from readily available natural α-amino acids through keeping of the existing chiral α-carbon. However, it is a great challenge to construct them under mild conditions. In this paper, 83 unnatural chiral α-amino acids were prepared at room temperature under visible-light assistance. The protocol uses two readily available genetically coded proteinogenic amino acids, L-aspartic acid and glutamic acid derivatives as the chiral sources and radical precursors, olefins, alkynyl and alkenyl sulfones, and 2-isocyanobiphenyl as the radical acceptors, and various unnatural chiral α-amino acids were prepared in good to excellent yields. The simple protocol, mild conditions, fast reactions, and high efficiency make the method an important strategy for synthesis of diverse unnatural chiral α-amino acids.

| S-EPMC4868990 | biostudies-literature

Stereocontrolled 1,3-nitrogen migration to access chiral α-amino acids.

Project description:α-Amino acids are essential for life as building blocks of proteins and components of diverse natural molecules. In both industry and academia, the incorporation of unnatural amino acids is often desirable for modulating chemical, physical and pharmaceutical properties. Here we report a protocol for the economical and practical synthesis of optically active α-amino acids based on an unprecedented stereocontrolled 1,3-nitrogen shift. Our method employs abundant and easily accessible carboxylic acids as starting materials, which are first connected to a nitrogenation reagent, followed by a highly regio- and enantioselective ruthenium- or iron-catalysed C(sp3)-H amination. This straightforward method displays a very broad scope, providing rapid access to optically active α-amino acids with aryl, allyl, propargyl and alkyl side chains, and also permits stereocontrolled late-stage amination of carboxylic-acid-containing drugs and natural products.

| S-EPMC7612692 | biostudies-literature

Simplifying the Synthesis of Nonproteinogenic Amino Acids via Palladium-Catalyzed δ-Methyl C-H Olefination of Aliphatic Amines and Amino Acids.

Project description:Transition metal-catalyzed directing group assisted C-H functionalizations provide a straightforward access to a wide variety of nonproteinogenic amino acids. While altering the side chain of an existing natural amino acids is one way, introducing a functional group to an aliphatic amine to synthesize versatile unnatural amino acids is another exciting avenue. In this work, we explore both the possibilities by the palladium-catalyzed δ-C(sp3)-H olefination of aliphatic amines and amino acids. A diverse substrate scope including sequential difunctionalizations followed by post synthetic transformations were achieved to understand the applicability of the current protocol. An in-depth mechanistic study was carried out to learn the mode of the reaction pathway.

| S-EPMC10369672 | biostudies-literature

Topological Water Network Analysis Around Amino Acids.

Project description:Water molecules play a key role in protein stability, folding, function and ligand binding. Protein hydration has been studied using free energy perturbation algorithms. However, the study of protein hydration without free energy calculation is also an active field of research. Accordingly, topological water network (TWN) analysis has been carried out instead of free energy calculation in the present work to investigate hydration of proteins. Water networks around 20 amino acids in the aqueous solution were explored through molecular dynamics (MD) simulations. These simulation results were compared with experimental observations. Water molecules from the protein data bank structures showed TWN patterns similar to MD simulations. This work revealed that TWNs are effected by the surrounding environment. TWNs could provide valuable clues about the environment around amino acid residues in the proteins. The findings from this study could be exploited for TWN-based drug discovery and development.

| S-EPMC6681432 | biostudies-literature

Nanoparticle-based Chemiluminescence for Chiral Discrimination of Thiol-Containing Amino Acids.

Project description:The ability to recognize the molecular chirality of enantiomers is extremely important owing to their critical role in drug development and biochemistry. Convenient discrimination of enantiomers has remained a challenge due to lack of unsophisticated methods. In this work, we have reported a simple strategy for chiral recognition of thiol-containing amino acids including penicillamine (PA), and cysteine (Cys). We have successfully designed a nanoparticle-based chemiluminescence (CL) system based on the reaction between cadmium telluride quantum dots (CdTe QDs) and the enantiomers. The different interactions of CdTe QDs with PA enantiomers or Cys enantiomers led to different CL intensities, resulting in the chiral recognition of these enantiomers. The developed method showed the ability for determination of enantiomeric excess of PA and Cys. It has also obtained an enantioselective concentration range from 1.15 to 9.2 mM for PA. To demonstrate the potential application of this method, the designed platform was applied for the quantification of PA in urine and tablet samples. For the first time, we presented a novel practical application of nanoparticle-based CL system for chiral discrimination.

| S-EPMC6143635 | 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