Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cascade Aryne Aminoarylation for Biaryl Phenol Synthesis.

ABSTRACT: We describe a transition metal-free approach to hindered 3-amino-2-aryl phenols through a cascade nucleophilic addition / Smiles-Truce rearrangement of a functionalized Kobayashi aryne precursor. Under anionic conditions, secondary alkyl amines add to the aryne intermediate to set up an aryl transfer from a neighboring sulfonate group. The use of a sulfonate, rather than the more typical sulfonamide, enables access to phenolic biaryl products that are important motifs in natural products and pharmaceuticals.

SUBMITTER: Das A

PROVIDER: S-EPMC11002935 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Cascade Aryne Aminoarylation for Biaryl Phenol Synthesis.

Das Aniruddha A Myers Danielle L DL Ganesh Venkataraman V Greaney Michael F MF

Organic letters 20240321 13

We describe a transition metal-free approach to hindered 3-amino-2-aryl phenols through a cascade nucleophilic addition / Smiles-Truce rearrangement of a functionalized Kobayashi aryne precursor. Under anionic conditions, secondary alkyl amines add to the aryne intermediate to set up an aryl transfer from a neighboring sulfonate group. The use of a sulfonate, rather than the more typical sulfonamide, enables access to phenolic biaryl products that are important motifs in natural products and pha ...[more]

PMID: 38512156

Similar Datasets

The Phenol-Ene Reaction: Biaryl Synthesis via Trapping Reactions between HDDA-Generated Benzynes and Phenolics.

Project description:Benzynes produced thermally by the cycloisomerization of triyne-containing precursors [i.e., by the hexadehydro-Diels-Alder (HDDA) reaction] react with phenols at the carbon ortho to the hydroxyl in an enelike fashion. Following tautomerization of the intermediate cyclohexadienones, this produces biaryl derivatives. DFT calculations of model reactions support this mechanistic interpretation. Substituted, unsymmetrical phenols and bis-phenols react in a fashion that can be explained by engagement of the most readily available (non-hydrogen-bonded) hydroxyl in the phenol-ene process.

| S-EPMC5107112 | biostudies-literature

The mechanism of the triple aryne-tetrazine reaction cascade: theory and experiment.

Project description:This article describes an experimental and computational investigation on the possible aryne reactivity modes in the course of the reaction of two highly energetic molecules, an aryne and a 1,2,4,5-tetrazine. Beyond the triple aryne-tetrazine (TAT) reaction, it was observed that combinations of several reactivity modes afford several heterocyclic compounds. Density Functional Theory (DFT) calculations of competition between a second Diels-Alder reaction and the nucleophilic addition pathways indicates the latter to be more favorable. Crossover experiments and computational study of the proton transfer step reveal that the reaction proceeds intermolecularly with the assistance of a water molecule, rather than intramolecularly. The resulting enamine intermediate was found to undergo either a stepwise formal [2 + 2] or [4 + 2] cycloaddition, and their energetic profiles were compared against each other. Isolation of an ene-product and a rearranged product shows the potential competition with oxidation/desaturation. These studies show how multiple arynes react with a highly reactive starting material and provide guidance for future applications of aryne-based multicomponent cascade reactions.

| S-EPMC6238107 | biostudies-literature

1,2-Bis(arylthio)arene synthesis via aryne intermediates.

Project description:Lithium 1,1-diadamantylamide (LDAM) base-promoted insertion of arynes into disulfide S-S bonds is described. After generation of arynes from readily available aryl halides and triflates, reactions with diaryl and diisopropyl disulfides afford the insertion products in moderate to excellent yields. Use of 1-cyclohexenyl triflate gave an excellent yield of 1,2-bis(phenylthio)cyclohexene.

| S-EPMC6896799 | biostudies-literature

Synthesis of Phenol-Hydrazide-Appended Tetraphenylethenes as Novel On-Off-On Cascade Sensors of Copper and Glutathione.

Project description:This study reports the synthesis of novel fluorescent probes, phenol-hydrazide-appended tetraphenylethenes (TPEs I and II), and explores their photochemical properties. The probes exhibit aggregation-induced emission (AIE) in increasing water content, as observed using fluorescence spectroscopy. Further investigation with UV-vis and fluorescence techniques revealed their potential as ion sensors. Both TPE I and TPE II act as "turn-off" sensors for Cu2+ ions, showing decreased fluorescence intensity in their presence. Their limit of detection (LOD) and association constant (K a) for Cu2+ were found to be comparable at 747 nM/597 nM, and 2.46 × 105 M-1/2/1.78 × 105 M-1/2, respectively. Moreover, the quantum yields of TPE I and TPE II were also calculated and found to be 0.651 and 0.325, respectively. Interestingly, these probes also function as "turn-on" sensors for glutathione (GSH) in the presence of copper. This means their fluorescence can be reversibly switched off and on by alternating CuCl2 and GSH additions. Moreover, the LOD values for GSH with TPE II-Cu2+ were calculated to be 544 nM. In addition, the investigation also employed visual analysis to assess the color alterations of TPEs on filter paper and in real water samples. Overall, this research introduces promising new probes with potential applications in copper ion detection and biomolecule glutathione sensing in real water samples.

| S-EPMC11191134 | biostudies-literature

Synthesis of 1,2-Bis(trifluoromethylthio)arenes via Aryne Intermediates.

Project description:A general method for synthesis of 1,2-bis-trifluoromethylthioarenes has been developed. Arynes generated from silyl aryl triflates or halides react with bis(trifluoromethyl)disulfide to afford 1,2-bis-trifluoromethylthioarenes. Aryl, alkyl, ester, halide, and methoxy functionalities are compatible with reaction conditions. Use of bis(perfluoroaryl)disulfides gave moderate yields of aryne disulfenylation or cyclization to fluorinated dibenzothiophenes.

| S-EPMC5716473 | biostudies-literature

Palladium-catalyzed synthesis of 9-fluorenylidenes through aryne annulation.

Project description:The palladium-catalyzed annulation of arynes by substituted o-halostyrenes produces substituted 9-fluorenylidenes in good yields. This methodology provides this important carbocyclic ring system in a single step, which involves the generation of two new carbon-carbon bonds, occurs under relatively mild reaction conditions, and tolerates a variety of functional groups, including cyano, ester, aldehyde, and ketone groups.

| S-EPMC2731569 | biostudies-literature

General method for functionalized polyaryl synthesis via aryne intermediates.

Project description:A method for base-promoted arylation of arenes and heterocycles by aryl halides and aryl triflates is described. Additionally, in situ electrophilic trapping of ArLi intermediates generated in the reaction of benzyne with deprotonated arenes or heterocycles has been developed, providing rapid and easy access to a wide range of highly functionalized polyaryls. Base-promoted arylation methodology complements transition-metal-catalyzed direct arylation and allows access to structures that are not easily accessible via other direct arylation methods. The reactions are highly functional-group tolerant, with alkene, ether, dimethylamino, trifluoromethyl, ester, cyano, halide, hydroxyl, and silyl functionalities compatible with reaction conditions.

| S-EPMC4227807 | biostudies-literature

One-Pot, Three-Aryne Cascade Strategy for Naphthalene Formation from 1,3-Diynes and 1,2-Benzdiyne Equivalents.

Project description:Here we disclose a cascade strategy for naphthyne formation that capitalizes on the traditional benzyne generation (i.e., from an ortho-silyl aryl triflate) and the thermal hexadehydro-Diels-Alder (HDDA) reaction. In this transformation, three distinct aryne species work in tandem, two of which can be formally considered as a 1,2-benzidyne, and each undergoes a different type of trapping event. Many examples were explored by varying the naphthyne capture chemistry as well as the 1,2-benzdiyne equivalent. This strategy enables rapid construction of various naphthalene products and has potential for the synthesis of extended polycyclic arenes.

| S-EPMC6933537 | biostudies-literature

Enantio-relay catalysis constructs chiral biaryl alcohols over cascade Suzuki cross-coupling-asymmetric transfer hydrogenation.

Project description:The construction of chiral biaryl alcohols using enantio-relay catalysis is a particularly attractive synthetic method in organic synthesis. However, overcoming the intrinsic incompatibility of distinct organometallic complexes and the reaction conditions used are significant challenges in asymmetric catalysis. To overcome these barriers, we have taken advantage of an enantio-relay catalysis strategy and a combined dual-immobilization approach. We report the use of an imidazolium-based organopalladium-functionalized organic-inorganic hybrid silica and ethylene-coated chiral organoruthenium-functionalized magnetic nanoparticles to catalyze a cascade Suzuki cross-coupling-asymmetric transfer hydrogenation reaction to prepare chiral biaryl alcohols in a two-step, one-pot process. As expected, the site-isolated active species, salient imidazolium phase-transfer character and high ethylene-coated hydrophobicity can synergistically boost the catalytic performance. Furthermore, enantio-relay catalysis has the potential to efficiently prepare a variety of chiral biaryl alcohols. Our synthetic strategy is a general method that shows the potential of developing enantio-relay catalysis towards environmentally benign and sustainable organic synthesis.

| S-EPMC5381470 | biostudies-literature

Solid-Phase Synthesis of Biaryl Cyclic Lipopeptides Derived from Arylomycins.

Project description:An efficient approach for the solid-phase synthesis of N-methylated tailed biaryl cyclic lipopeptides based on the structure of arylomycins was established. Each of these analogues incorporates an N-terminal linear lipopeptide attached to a biaryl cyclic tripeptide containing a Phe-Tyr, a Tyr-Tyr, or a His-Tyr linkage. This methodology first involved an intramolecular Suzuki-Miyaura arylation of a linear peptidyl resin incorporating the corresponding halogenated amino acid at the N-terminus and a boronotyrosine at the C-terminus. After N-methylation of the resulting biaryl cyclic peptidyl resin, the N-methylated lipopeptidyl tail was then assembled. The biaryl cyclic lipopeptides were purified and characterized.

| S-EPMC7496001 | 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