Browse
Submit Data
Databases
API
Help

Dataset Information

8 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore.

ABSTRACT: The stereoselective synthesis of truxillic bis-amino esters from polyfunctional oxazolones is reported. The reaction of 4-((Z)-arylidene)-2-(E)-styryl-5(4H)-oxazolones 2 with Pd(OAc)₂ resulted in ortho-palladation and the formation of a dinuclear open-book complexes 3 with carboxylate bridges, where the Pd atom is C^N bonded to the oxazolone. In 3 the two exocyclic C=C bonds of the oxazolone are in a face-to-face arrangement, which is optimal for their [2 + 2] photocycloaddition. Irradiation of dimers 3 in CH₂Cl₂ solution with blue light (465 nm) promoted the chemo- and stereoselective [2 + 2] photocycloaddition of the exocyclic C=C bonds and the formation of cyclobutane-containing ortho-palladated complexes 4. Treatment of 4 with CO in a MeOH/NCMe mixture promoted the methoxycarbonylation of the palladated carbon and the release of the corresponding ortho-functionalized 1,3-diaminotruxillic bis-amino esters 5 as single isomers.

SUBMITTER: Urriolabeitia EP

PROVIDER: S-EPMC7277947 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Synthesis and antioxidant evaluation of enantiomerically pure bis-(1,2,3-triazolylmethyl)amino esters from modified α-amino acids.

Project description:The efforts for synthesis of enantiomerically pure bis-(1,2,3-triazolylmethyl)amino esters 6 are reported in good yields from an in situ generated α-azidomethyl ketone. Optimum experimental conditions were established for preparation of α-halomethyl ketones 10 and α-N,N-dipropargylamino esters 11, all derived from α-amino acids. The starting materials reacted under conventional click chemistry conditions, revealing a specific reactivity of bromomethyl ketones over chloromethyl ketones. The antioxidant activity of compounds 6 was assayed by DPPH method. The compound 6c with an IC50 of 75.57 ± 1.74 μg mL(-1) was the most active. Technically, this methodology allows the preparation of a combinatorial library of analogues with different structural characteristics depending on the nature of the modified α-amino acids employed in the synthesis.

| S-EPMC4216715 | biostudies-literature

A method for the synthesis of unsymmetric bisphosphoric analogs of α-amino acids.

Project description:Herein, we describe the first universal strategy for the synthesis of unsymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogs of N-protected 1-aminobisphosphonates. The proposed user-friendly procedure, based on a one-pot reaction of the α-ethoxy derivatives of phosphorus analogs of protein and non-protein α-amino acids with triphenylphosphonium tetrafluoroborate and an appropriate phosphorus nucleophile (diethyl phenylphosphonite or methyl diphenylphosphinite), provides good to very good yields of 53-91% under mild catalyst-free conditions (temperature: rt to 40 °C, time: 1 to 6 hours). The progress of the transformation, running through the corresponding phosphonium salt as a reactive intermediate, was monitored by 31P NMR spectroscopy, which is a convenient tool for the identification of the transient species formed here. In this paper, we present the full characteristics of the spectroscopic properties of all 13 synthesized models of structurally diverse N-protected unsymmetric bisphosphoric analogs of α-amino acids. Therefore, these results contribute to increasing the practical applicability of our recently reported synthesis protocol of symmetric models of α-aminobisphosphonates derivatives and thus justify its universality.

| S-EPMC10288832 | biostudies-literature

Biocatalytic, Stereoselective Deuteration of α-Amino Acids and Methyl Esters.

Project description:α-2H amino acids are valuable precursors toward labeled pharmaceutical agents and tools for studying biological systems; however, these molecules are costly to purchase and challenging to synthesize in a site- and stereoselective manner. Here, we show that an α-oxo-amine synthase that evolved for saxitoxin biosynthesis, SxtA AONS, is capable of producing a range of α-2H amino acids and esters site- and stereoselectively using D2O as the deuterium source. Additionally, we demonstrate the utility of this operationally simple reaction on preparative scale in the stereoselective chemoenzymatic synthesis of a deuterated analog of safinamide, a drug used to treat Parkinson's disease.

| S-EPMC8382264 | biostudies-literature

Decarboxylative allylation of amino alkanoic acids and esters via dual catalysis.

Project description:A combination of photoredox and palladium catalysis has been employed to facilitate the room temperature decarboxylative allylation of recalcitrant ?-amino and phenylacetic allyl esters. This operationally simple process produces CO2 as the only byproduct and provides direct access to allylated alkanes. After photochemical oxidation, the carboxylate undergoes radical decarboxylation to site-specifically generate radical intermediates which undergo allylation. A radical dual catalysis mechanism is proposed. Free phenylacetic acids were also allylated utilizing similar reactions conditions.

| S-EPMC4183636 | biostudies-literature

Correction to "Development of Fmoc-Protected Bis-Amino Acids toward Automated Synthesis of Highly Functionalized Spiroligomers".

Project description: Not available

| S-EPMC9942684 | biostudies-literature

Mutant p53 regulates serine-glycine synthesis and essential amino acids intake

Project description:This SuperSeries is composed of the SubSeries listed below.

2023-10-06 | GSE214494 | GEO

Asymmetric synthesis of anti-β-amino-α-hydroxy esters via dynamic kinetic resolution of β-amino-α-keto esters.

Project description:A method for the asymmetric synthesis of enantioenriched anti-α-hydroxy-β-amino acid derivatives by enantioconvergent reduction of the corresponding racemic α-keto esters is presented. The requisite α-keto esters are prepared via Mannich addition of ethyl diazoacetate to imines followed by oxidation of the diazo group with Oxone. Implementation of a recently developed dynamic kinetic resolution of β-substituted-α-keto esters via Ru(II)-catalyzed asymmetric transfer hydrogenation provides the title motif in routinely high diastereo- and enantioselectivity.

| S-EPMC3766400 | biostudies-literature

Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(?-cyclodextrin) Copper Complexes.

Project description:It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(?-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the "back-to-back" bisCD complex CuL(1) favoured higher catalytic efficiency and more pronounced enantioselectivity than the "face-to-face" complex CuL(2). The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL(1), which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL(1), even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

| S-EPMC4768151 | biostudies-literature

Synthesis of Diaryl Hydroxyl Dicarboxylic Acids from Amino Acids.

Project description:Herein we report a unique method for preparing diaryl hydroxyl dicarboxylic acids in a diastereospecific manner. The three-component reaction occurs between amino acid, aromatic aldehyde, and primary alcohol in alkaline solutions under microwave-assisted conditions. The dicarboxylic acids are isolated as sodium salts in high yields (up to 77%) by direct precipitation from the reaction solution. The experimental results suggest that the diastereospecificity originates from a [3,3]-sigmatropic rearrangement followed by a sodium-assisted hydride transfer. As further shown, the previously unreported dicarboxylic acids are easily turned into corresponding δ-lactones.

| S-EPMC7497638 | biostudies-literature

Synthesis of Endocyclic Cycloalkyne Amino Acids.

Project description:"Click-ligation" is a widely adopted and valuable means to ligate biomolecules whereby two appended biologically inert moieties, such as alkynes and azides, link by cycloaddition. For terminal alkynes, Cu+1 catalysis is required which degrades oligonucleotides by catalyzing their hydrolysis but is also physiologically incompatible. The smallest activated alkynes that do not require Cu+1 catalysis are cyclooctynes or dibenzo-cyclooctynes. For this purpose, there are commercially available nucleosides and amino acids that are appended to these moieties. However, these structures are bulky, dissimilar to native amino acids, and when incorporated within biological molecules could likely perturb native structural configuration. Presented are the syntheses of structural analogues of proline with an inserted propargyl moiety within a series of ring sizes. Moreover, a synthetic pathway to medium-size ring heterocycloalkynes mediated by using mild Mitsunobu conditions in tandem with a Nicholas-related strategy for cyclization is introduced. Avoiding the usual harsh acidic conditions for the Nicholas reaction allows improved functional group compatibility.

| S-EPMC8928491 | 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