Asymmetric autocatalysis induced by meteoritic amino acids with hydrogen isotope chirality.
Ontology highlight
ABSTRACT:
SUBMITTER: Kawasaki T
PROVIDER: S-EPMC2898652 | biostudies-literature | 2009 Aug
REPOSITORIES: biostudies-literature
Publications
Asymmetric autocatalysis induced by meteoritic amino acids with hydrogen isotope chirality.
Kawasaki Tsuneomi T Shimizu Masako M Nishiyama Daisuke D Ito Masateru M Ozawa Hitomi H Soai Kenso K
Chemical communications (Cambridge, England) 20090624 29
Achiral meteoritic amino acids, glycine and alpha-methylalanine, with hydrogen isotope (D/H) chirality, acted as the source of chirality in asymmetric autocatalysis with amplification of ee to afford highly enantioenriched 5-pyrimidyl alkanols. ...[more]
Similar Datasets
Project description:The organic compounds found in carbonaceous chondrite meteorites provide insight into primordial solar system chemistry. Evaluating the formation and decomposition mechanisms of meteoritic amino acids may aid our understanding of the origins of life and homochirality on Earth. The amino acid glycine is widespread in meteorites and other extraterrestrial environments; other amino acids, such as isovaline, are found with enantiomeric excesses in some meteorites. The relationship between meteoritic amino acids and other compounds with similar molecular structures, such as aliphatic monoamines and monocarboxylic acids is unclear; experimental results evaluating the decomposition of amino acids have produced inconclusive results about the preferred pathways, reaction intermediates, and if the conditions applied may be compatible with those occurring inside meteoritic parent bodies. In this work, we performed extensive tandem metadynamics, umbrella sampling, and committor analysis to simulate the neutral mild hydrothermal decomposition mechanisms of glycine and isovaline and put them into context for the origins of meteoritic organic compounds. Our ab initio simulations aimed to determine free energy profiles and decomposition pathways for glycine and isovaline. We found that under our modeled conditions, methylammonium, glycolic acid, and sec-butylamine are the most likely decomposition products. These results suggest that meteoritic aliphatic monocarboxylic acids are not produced from decomposition of meteoritic amino acids. Our results also indicate that the decomposition of L-isovaline prefers an enantioselective pathway resulting in the production of (S)-sec-butylamine.
| S-EPMC7340093 | biostudies-literature
Project description:We describe an approach for accurate quantitation of global protein dynamics in Caenorhabditis elegans. We adapted stable-isotope labeling with amino acids in cell culture (SILAC) for nematodes by feeding worms a heavy lysine- and heavy arginine-labeled Escherichia coli strain and report a genetic solution to elminate the problem of arginine-to-proline conversion. Combining our approach with quantitative proteomics methods, we characterized the heat-shock response in worms.
| S-EPMC3184259 | biostudies-literature
Project description:Tripodal chiral ligands containing amino acid residues and salicyl-acylhydrazone units were synthesized and used to obtain coordination cages through deprotonation and coordination to gallium. These coordination cages have Ga3L2 stoichiometry and pinwheel geometry with two types of chiral centers built into their walls: stereogenic centers at the amino acid backbones and stereoselectively induced centers at metal ions. The pinwheel geometry is unique among analogous cages and originates from the partial flexibility of the ligands. Despite the flexibility, the ligands induce the chirality of metal centers in a highly stereoselective way, leading to the formation of cages that are single diastereoisomers. It has also been demonstrated that stereoselectivity is a unique feature of cage geometry and leads to effective chiral self-sorting: homochiral cages can be obtained selectively from the mixtures of racemic ligands. The configuration of metal centers was determined by circular dichroism, TD DFT calculation, and X-ray crystallography.
| S-EPMC9490811 | biostudies-literature
Project description:Systematic enrichments of L-amino acids in meteorites is a strong indication that biological homochirality originated beyond Earth. Although still unresolved, stellar UV circularly polarized light (CPL) is the leading hypothesis to have caused the symmetry breaking in space. This involves the differential absorption of left- and right-CPL, a phenomenon called circular dichroism, which enables chiral discrimination. Here we unveil coherent chiroptical spectra of thin films of isovaline enantiomers, the first step towards asymmetric photolysis experiments using a tunable laser set-up. As analogues to amino acids adsorbed on interstellar dust grains, CPL-helicity dependent enantiomeric excesses of up to 2% were generated in isotropic racemic films of isovaline. The low efficiency of chirality transfer from broadband CPL to isovaline could explain why its enantiomeric excess is not detected in the most pristine chondrites. Notwithstanding, small, yet consistent L-biases induced by stellar CPL would have been crucial for its amplification during aqueous alteration of meteorite parent bodies.
| S-EPMC10250315 | biostudies-literature
Project description:Chiral isotactic polystyrenes induce the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde, affording the enantiomerically enriched pyrimidyl alkanol with the corresponding absolute configuration to that of cryptochiral polystyrenes in conjunction with asymmetric autocatalysis.
| S-EPMC2898645 | biostudies-literature
Project description:This report presents an overview of the family of naturally occurring 'vinylic' amino acids, namely those that feature a C-C double bond directly attached to the α-carbon, along the side chain. Strategies that have been brought to bear on the stereocontrolled synthesis of these olefinic amino acids are surveyed. The mechanistic diversity by which such 'vinylic triggers' can be actuated in a PLP (pyridoxal phosphate) enzyme active site is then highlighted by discussions of vinylglycine (VG), its substituted congeners, particularly AVG [4E-(2'-aminoethoxy)vinylglycine], and a naturally occurring VG-progenitor, SMM (S-methylmethionine).
| S-EPMC6029878 | biostudies-literature
Project description:Alpha-amino acids are the building blocks of proteins and are widely used as components of medicinally active molecules and chiral catalysts. Efficient chemo-enzymatic methods for the synthesis of enantioenriched alpha-amino acids have been developed, but it is still a challenge to obtain non-natural amino acids. Alkene hydrogenation is broadly useful for the enantioselective catalytic synthesis of many classes of amino acids, but it is not possible to obtain alpha-amino acids bearing aryl or quaternary alkyl alpha-substituents using this method. The Strecker synthesis-the reaction of an imine or imine equivalent with hydrogen cyanide, followed by nitrile hydrolysis-is an especially versatile chemical method for the synthesis of racemic alpha-amino acids. Asymmetric Strecker syntheses using stoichiometric amounts of a chiral reagent have been applied successfully on gram-to-kilogram scales, yielding enantiomerically enriched alpha-amino acids. In principle, Strecker syntheses employing sub-stoichiometric quantities of a chiral reagent could provide a practical alternative to these approaches, but the reported catalytic asymmetric methods have seen limited use on preparative scales (more than a gram). The limited utility of existing catalytic methods may be due to several important factors, including the relatively complex and precious nature of the catalysts and the requisite use of hazardous cyanide sources. Here we report a new catalytic asymmetric method for the syntheses of highly enantiomerically enriched non-natural amino acids using a simple chiral amido-thiourea catalyst to control the key hydrocyanation step. This catalyst is robust, without sensitive functional groups, so it is compatible with aqueous cyanide salts, which are safer and easier to handle than other cyanide sources; this makes the method adaptable to large-scale synthesis. We have used this new method to obtain enantiopure amino acids that are not readily prepared by enzymatic methods or by chemical hydrogenation.
| S-EPMC2778849 | biostudies-literature
Project description:Diisopropylzinc alkylation of pyrimidine aldehydes-the Soai reaction, with its astonishing attribute of amplifying asymmetric autocatalysis-occupies a unique position in organic chemistry and stands as an eminent challenge for mechanistic elucidation. A new paradigm of "mixed catalyst-substrate" experiments with pyrimidine and pyridine systems allows a disconnection of catalysis from autocatalysis, providing insights into the role played by reactant and alkoxide structure. The alkynyl substituent favorably tunes catalyst solubility, aggregation, and conformation while modulating substrate reactivity and selectivity. The alkyl groups and the heteroaromatic core play further complementary roles in catalyst aggregation and substrate binding. In the study of these structure-activity relationships, novel pyridine substrates demonstrating amplifying autocatalysis were identified. Comparison of three autocatalytic systems representing a continuum of nitrogen Lewis basicity strength suggests how the strength of N-Zn binding events is a predominant contributor toward the rate of autocatalytic progression.
| S-EPMC7597373 | biostudies-literature
Project description:Chemical reactions that lead to a spontaneous symmetry breaking or amplification of the enantiomeric excess are of fundamental interest in explaining the formation of a homochiral world. An outstanding example is Soai's asymmetric autocatalysis, in which small enantiomeric excesses of the added product alcohol are amplified in the reaction of diisopropylzinc and pyrimidine-5-carbaldehydes. The exact mechanism is still in dispute due to complex reaction equilibria and elusive intermediates. In situ high-resolution mass spectrometric measurements, detailed kinetic analyses and doping with in situ reacting reaction mixtures show the transient formation of hemiacetal complexes, which can establish an autocatalytic cycle. We propose a mechanism that explains the autocatalytic amplification involving these hemiacetal complexes. Comprehensive kinetic experiments and modelling of the hemiacetal formation and the Soai reaction allow the precise prediction of the reaction progress, the enantiomeric excess as well as the enantiomeric excess dependent time shift in the induction period. Experimental structural data give insights into the privileged properties of the pyrimidyl units and the formation of diastereomeric structures leading to an efficient amplification of even minimal enantiomeric excesses, respectively.
| S-EPMC7756584 | biostudies-literature
Project description:Asymmetric amplification induced in the Soai autocatalytic reaction by chiral initiators that are enantiomeric only by virtue of an isotope, e.g., -CH3 vs CD3-, is examined by spectroscopic, kinetic, and DFT modeling studies to help understand requirements for the emergence of biological homochirality. We find that the initiator inhibits the autocatalytic pathway at the outset of the reaction but ultimately provides the imbalance required for asymmetric amplification. This work provides clues in the ongoing search for prebiotically plausible versions of asymmetric autocatalysis.
| S-EPMC6026777 | biostudies-literature