Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates.

ABSTRACT: A metal-free route for the synthesis of biarenes has been developed. The approach is based on the photoextrusion of a phosphate moiety occurring upon irradiation of biaryl- and triaryl phosphates. The reaction involves an exciplex as the intermediate and it is especially suitable for the preparation of electron-rich biarenes.

SUBMITTER: Qrareya H

PROVIDER: S-EPMC7736689 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates.

Qrareya Hisham H Meazza Lorenzo L Protti Stefano S Fagnoni Maurizio M

Beilstein journal of organic chemistry 20201208

A metal-free route for the synthesis of biarenes has been developed. The approach is based on the photoextrusion of a phosphate moiety occurring upon irradiation of biaryl- and triaryl phosphates. The reaction involves an exciplex as the intermediate and it is especially suitable for the preparation of electron-rich biarenes. ...[more]

PMID: 33363669

Similar Datasets

Metal-Free Synthesis of 1,3-Disiloxanediols and Aryl Siloxanols.

Project description:The first example of metal-free oxidative hydrolysis of hydrido-siloxanes is reported. Both base-catalyzed and organocatalytic hydrolysis methods are demonstrated to transform 1,3-dihydrido-disiloxanes into 1,3-disiloxanediols. The first example of a chemoselective silane hydrolysis is demonstrated.

| S-EPMC6648610 | biostudies-literature

Transition Metal-Free Synthesis of Halobenzo[b]furans from O-Aryl Carbamates via o-Lithiation Reactions.

Project description:A straightforward and transition metal-free one-pot protocol to synthesize halobenzo[b]furans has been developed employing simple and easily available starting materials such as O-aryl carbamates and alkynylsulfones. The fine-tuning of the different steps involved was key to achieving a successful one-pot procedure. Initially, a directed ortho-lithiation process, which uses the carbamate as the directed metalation group, was crucial in providing access to O-2-alkynylaryl N,N-diethyl carbamates by a direct alkynylation of the o-lithiated carbamate, with arylsulfonylalkynes as electrophilic reagents. Cyclization of the generated o-alkynylaryl carbamates was successfully accomplished through a strategy involving in situ carbamate alkaline hydrolysis under conventional heating or microwave irradiation, coupled with a subsequent heterocyclization step delivering the desired benzo[b]furans. A wide variety of new halobenzo[b]furans has been synthesized and their utility has been demonstrated by their further transformation.

| S-EPMC8778012 | biostudies-literature

Transition-Metal-Free Synthesis of Unsymmetrical Diaryl Tellurides via SH2 Reaction of Aryl Radicals on Tellurium.

Project description:Although diaryl tellurides are parent organotellurium compounds, their synthesis methods, especially for unsymmetrical ones, are limited. This may be due to the instability of diaryl tellurides and their synthesis intermediates under reaction conditions. Radical reactions are known to exhibit excellent functional group selectivity; therefore, we focused on a bimolecular homolytic substitution (SH2) reaction between the aryl radical and diaryl ditelluride. Aryl radicals are generated from arylhydrazines in air and captured by diaryl ditellurides, resulting in a selective formation of unsymmetrical diaryl tellurides with high yields. The electronic effects of the substituents on both arylhydrazines and diaryl ditellurides on the SH2 reaction of tellurium are also discussed in detail.

| S-EPMC8839872 | biostudies-literature

Metal Free Bi(hetero)aryl Synthesis: A Benzyne Truce-Smiles Rearrangement.

Project description:A new benzyne transformation is described that affords versatile biaryl structures without recourse to transition-metal catalysis or stoichiometric amounts of organometallic building blocks. Aryl sulfonamides add to benzyne upon fluoride activation, and then undergo an aryl Truce-Smiles rearrangement to afford biaryls with sulfur dioxide extrusion. The reaction proceeds under simple reaction conditions and has excellent scope for the synthesis of sterically hindered atropisomeric biaryl amines.

| S-EPMC4819888 | biostudies-literature

Metal-free di- and tri-fluoromethylation of alkenes realized by visible-light-induced perylene photoredox catalysis.

Project description:Regioselective amino-difluoromethylation of aromatic alkenes via C(sp3)-CF2H and C(sp3)-N bond formation with the C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C moiety has been achieved in a single operation by visible-light photoredox catalysis. The combination of a shelf-stable and easy-to-handle sulfonium salt, S-difluoromethyl-S-di(p-xylyl)sulfonium tetrafluoroborate, and perylene catalysis is the key to the successful transformation. Furthermore, this noble metal-free protocol allows for the photocatalytic trifluoromethylation of alkenes.

| S-EPMC5628600 | biostudies-literature

Low-Temperature Continuous Flow Synthesis of Metal Ammonium Phosphates.

Project description:The synthesis of the high performance inorganic materials essential to the quality of modern day life is hindered by traditionalist attitudes and reliance on outdated methods such as batch syntheses. While continuous flow methods have been extensively adopted in pharmaceutical circles, they remain largely unexplored for the preparation of inorganic compounds, despite higher efficiency, safety and versatility. In this publication, we demonstrate a step-change for the synthesis of metal ammonium phosphates through conversion of the extant batch process to a low-temperature continuous regime, exhibiting a tenfold increase in throughput combined with a significant decrease in particle size.

| S-EPMC6131346 | biostudies-literature

Solvent- and transition metal-free amide synthesis from phenyl esters and aryl amines.

Project description:A general, economical, and environmentally friendly method of amide synthesis from phenyl esters and aryl amines was developed. This new method has significant advantages compared to previously reported palladium-catalyzed approaches. The reaction is performed transition metal- and solvent-free, using a cheap and environmentally benign base, NaH. This approach enabled us to obtain target amides in high yields with high atom economy.

| S-EPMC9059645 | biostudies-literature

Transition-metal-free synthesis of aryl 1-thioglycosides with arynes at room temperature.

Project description:A mild, convenient and transition-metal-free protocol for the synthesis of aryl 1-thioglycosides is presented via arynes generated in situ combined with glycosyl thiols in the presence of TBAF(tBuOH)4. The methodology provides a general and efficient way to prepare a series of functionalized thioglycosides in good to excellent yields with a perfect control of the anomeric configuration at room temperature. In addition, the reaction conditions tolerate a variety of the pentoses and hexoses, and the reaction also performs smoothly on protected monosaccharides and disaccharides.

| S-EPMC9037310 | biostudies-literature

Inhibition of lipid-linked oligosaccharide synthesis by aryl phosphates.

Project description:Our previous work has shown that phenyl phosphate acts as an exogenous substrate for GDP-mannose:dolichyl phosphate mannosyltransferase in rat liver microsomal fractions to give rise to phenyl phosphate beta-D-mannose, a compound which, unlike Dol-P-Man (dolichyl phosphate beta-D-mannose), cannot act as mannose donor for further mannose-adding reactions in microsomal fractions. The study has now been extended to the action of various aryl phosphates and structurally related compounds on several other glycosyltransferase systems in the microsomal fractions. (1) Examination of the ability of these compounds to accept sugars from various sugar nucleotides indicated that the individual compounds have specificity as sugar acceptors. Thus phenyl phosphate acted as an effective acceptor for both mannose and glucose, whereas benzenephosphonic acid was active only in accepting mannose. p-Nitrophenyl phosphate was a more effective glucose acceptor than phenyl phosphate, but had only 8% of the mannose-accepting activity of phenyl phosphate. (2) Phenyl phosphate had an inhibitory effect on the transfer of mannose form GDP-mannose to lipid-linked oligosaccharides and to glycoproteins in rat liver microsomal fractions. The inhibition depended on the concentration of phenyl phosphate and on the extent of inhibition of Dol-P-Man synthesis. It is proposed that phenyl phosphate has a direct effect on the synthesis of Dol-P-Man and that its inhibition of synthesis of lipid-linked oligosaccharides and glycoproteins could be a consequence of this effect.

| S-EPMC1162969 | biostudies-other

Tetrabutylammonium Bromide-Promoted Metal-Free, Efficient, Rapid, and Scalable Synthesis of N-Aryl Amines.

Project description:A rapid, transition metal-free, high-yielding, tetrabutylammonium bromide-promoted method of N-arylation is reported within. The optimized conditions tolerated a wide range of secondary amines and was equally effective with bromo- and chlorobenzene-including substituted aryl halides. The developed method is found to be effective for N-arylation when compared to earlier methods which involve harsh conditions, transition metals, lack of scalability, and long reaction times. Our method utilizes conventional heating only; it is readily scalable; and the products are facile to purify.

| S-EPMC6166220 | 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