Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A visible-light mediated three-component radical process using dithiocarbamate anion catalysis.

ABSTRACT: We report a photoinduced three-component radical process, which couples readily available alkyl chlorides, maleimides, and heteroaromatic fragments to rapidly generate complex chiral products with high diastereocontrol. This method generates radicals via an S_N2-based photochemical catalytic mechanism, which is not reliant on the redox properties of the precursors. It therefore grants access to open-shell intermediates from substrates that would be incompatible with or inert to classical radical-generating strategies. The redox-neutral conditions of this process make it tolerant of redox-sensitive substrates and allow the installation of multiple biologically relevant heterocycles within the cascade products.

SUBMITTER: Cuadros S

PROVIDER: S-EPMC6553376 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A visible-light mediated three-component radical process using dithiocarbamate anion catalysis.

Cuadros Sara S Horwitz Matthew A MA Schweitzer-Chaput Bertrand B Melchiorre Paolo P

Chemical science 20190430 21

We report a photoinduced three-component radical process, which couples readily available alkyl chlorides, maleimides, and heteroaromatic fragments to rapidly generate complex chiral products with high diastereocontrol. This method generates radicals via an SN2-based photochemical catalytic mechanism, which is not reliant on the redox properties of the precursors. It therefore grants access to open-shell intermediates from substrates that would be incompatible with or inert to ...[more]

PMID: 31293731

Similar Datasets

Visible-Light-Mediated Three-Component Cascade Sulfonylative Annulation.

Project description:Visible-light-promoted cascade radical cyclization for the synthesis of sulfonylated benzimidazo/indolo[2,1-a]iso-quinolin-6(5H)-ones has been reported. The reaction provides transition-metal-free and expeditious access to sulfonylated polyaromatics. The use of sodium metabisulfite as a SO2 surrogate and the rapid generation of molecular complexity using a three-component photochemical protocol are the salient features of this reaction manifold.

| S-EPMC9434776 | biostudies-literature

General Method for Enantioselective Three-Component Carboarylation of Alkenes Enabled by Visible-Light Dual Photoredox/Nickel Catalysis.

Project description:A visible-light-promoted photoredox/nickel protocol for the enantioselective three-component carboarylation of alkenes with tertiary and secondary alkyltrifluoroborates and aryl bromides is described. This redox-neutral protocol allows for facile and divergent access to a wide array of enantioenriched β-alkyl-α-arylated carbonyls, phosphonates, and sulfones in high yields and excellent enantioselectivities from readily available starting materials. We also report a modular and enantioselective synthesis of flurbiprofen analogs and piragliatin lead compound to demonstrate synthetic utility. Experimental and computational mechanistic studies were performed to gain insights into the mechanism and origin of chemo- and enantioselectivity.

| S-EPMC8131407 | biostudies-literature

Metal-free, visible-light induced enantioselective three-component dicarbofunctionalization and oxytrifluoromethylation of enamines via chiral phosphoric acid catalysis.

Project description:Using diverse carbon-centered radical precursors and electron-rich (hetero)aromatics and alcohols as nucleophiles, a visible-light driven chiral phosphoric acid (CPA) catalyzed asymmetric intermolecular, three-component radical-initiated dicarbofunctionalization and oxytrifluoromethylation of enamines was developed, which provides a straightforward access to chiral arylmethylamines, aza-hemiacetals and γ-amino acid derivatives with excellent enantioselectivity. As far as we know, this is the first example of constructing a chiral C-O bond using simple alcohols via visible-light photocatalysis. Chiral phosphoric acid played multiple roles in the reaction, including controlling the reaction stereoselectivity and promoting the generation of radical intermediates by activating Togni's reagent. Mechanistic studies also suggested the importance of the N-H bond of the enamine and indole for the reactions.

| S-EPMC8790774 | biostudies-literature

Bromine radical as a visible-light-mediated polarity-reversal catalyst.

Project description:Polarity-reversal catalysts enable otherwise sluggish or completely ineffective reactions which are characterized by unfavorable polar effects between radicals and substrates. We herein disclose that when irradiated by visible light, bromine can behave as a polarity-reversal catalyst. Hydroacylation of vinyl arenes, a three-component cascade transformation and deuteration of aldehydes were each achieved in a metal-free manner without initiators by using inexpensive N-bromosuccinimide as the precatalyst. Light is essential to generate and maintain the active bromine radical during the reaction process. Another key to success is that HBr can behave as an effective hydrogen donor to turn over the catalytic cycles.

| S-EPMC8243021 | biostudies-literature

Radical Addition of Dihydroquinoxalin-2-ones to Trifluoromethyl Ketones under Visible-Light Photoredox Catalysis.

Project description:A visible-light photocatalytic radical addition reaction of dihydroquinoxalin-2-ones to trifluoromethyl ketones has been established using Ru(bpy)3Cl2 as photocatalyst, acetonitrile as solvent, and HP Single Blue LED as the source of light. The reaction provides a straightforward approach to the synthesis of dihydroquinoxalin-2-ones bearing a trifluoromethyl-substituted tertiary alcohol moiety in moderate to good yields under mild conditions.

| S-EPMC9295130 | biostudies-literature

Regioselective Radical Cascade Cyclizations of Alkyne-Tethered Cyclohexadienones with Chalcogenides under Visible-Light Catalysis.

Project description:Herein, we demonstrated a silver/K2S2O8-mediated highly regio- and diastereoselective 6/5-exo trig radical cascade cyclization of alkyne-tethered cyclohexadienones with sulfonyl hydrazides or sodium sulfinates and subsequent selenation to access 6,6-dihydrochromenone and 6,5-fused tetrahydro benzofuranone derivatives. This reaction protocol features high functional group compatibility and has a wide substrate scope providing a variety of dihydrochromenones and tetrahydro benzofuranone derivatives in good to excellent yields. The reaction proceeds via the attack of a sulfonyl radical to alkyne over the activated Michael acceptor. The TEMPO quenching experiment implies the presence of a radical intermediate. Further synthetic versatility of 6,6- and 5,6-fused derivatives is also showcased.

| S-EPMC10552108 | biostudies-literature

Synthesis of aryl sulfides via radical-radical cross coupling of electron-rich arenes using visible light photoredox catalysis.

Project description:Electron-rich arenes react with aryl and alkyl disulfides in the presence of catalytic amounts of [Ir(dF(CF3)ppy)2(dtbpy)]PF6 and (NH4)2S2O8 under blue light irradiation to yield arylthiols. The reaction proceeds at room temperature and avoids the use of prefunctionalized arenes. Experimental evidence suggests a radical-radical cross coupling mechanism.

| S-EPMC6176842 | biostudies-literature

Visible Light-Mediated Monofluoromethylation/Acylation of Olefins by Dual Organo-Catalysis.

Project description:Monofluoromethyl (CH2F) motifs exhibit unique bioactivities and are considered privileged units in drug discovery. The radical monofluoromethylative difunctionalization of alkenes stands out as an appealing approach to access CH2F-containing compounds. However, this strategy remains largely underdeveloped, particularly under metal-free conditions. In this study, we report on visible light-mediated three-component monofluoromethylation/acylation of styrene derivatives employing NHC and organic photocatalyst dual catalysis. A diverse array of α-aryl-β-monofluoromethyl ketones was successfully synthesized with excellent functional group tolerance and selectivity. The mild and metal-free CH2F radical generation strategy from NaSO2CFH2 holds potential for further applications in fluoroalkyl radical chemistry.

| S-EPMC10892033 | biostudies-literature

Formation and degradation of strongly reducing cyanoarene-based radical anions towards efficient radical anion-mediated photoredox catalysis.

Project description:Cyanoarene-based photocatalysts (PCs) have attracted significant interest owing to their superior catalytic performance for radical anion mediated photoredox catalysis. However, the factors affecting the formation and degradation of cyanoarene-based PC radical anion (PC•‒) are still insufficiently understood. Herein, we therefore investigate the formation and degradation of cyanoarene-based PC•‒ under widely-used photoredox-mediated reaction conditions. By screening various cyanoarene-based PCs, we elucidate strategies to efficiently generate PC•‒ with adequate excited-state reduction potentials (Ered*) via supra-efficient generation of long-lived triplet excited states (T1). To thoroughly investigate the behavior of PC•‒ in actual photoredox-mediated reactions, a reductive dehalogenation is carried out as a model reaction and identified the dominant photodegradation pathways of the PC•‒. Dehalogenation and photodegradation of PC•‒ are coexistent depending on the rate of electron transfer (ET) to the substrate and the photodegradation strongly depends on the electronic and steric properties of the PCs. Based on the understanding of both the formation and photodegradation of PC•‒, we demonstrate that the efficient generation of highly reducing PC•‒ allows for the highly efficient photoredox catalyzed dehalogenation of aryl/alkyl halides at a PC loading as low as 0.001 mol% with a high oxygen tolerance. The present work provides new insights into the reactions of cyanoarene-based PC•‒ in photoredox-mediated reactions.

| S-EPMC9822901 | biostudies-literature

Visible-light mediated catalytic asymmetric radical deuteration at non-benzylic positions.

Project description:Site- and enantioselective incorporation of deuterium into organic compounds is of broad interest in organic synthesis, especially within the pharmaceutical industry. While catalytic approaches relying on two-electron reaction manifolds have allowed for stereoselective delivery of a formal deuteride (D-) or deuteron (D+) at benzylic positions, complementary strategies that make use of one-electron deuterium atom transfer and target non-benzylic positions remain elusive. Here we report a photochemical approach for asymmetric radical deuteration by utilizing readily available peptide- or sugar-derived thiols as the catalyst and inexpensive deuterium oxide as the deuterium source. This metal-free platform enables four types of deuterofunctionalization reactions of exocyclic olefins and allows deuteration at non-benzylic positions with high levels of enantioselectivity and deuterium incorporation. Computational studies reveal that attractive non-covalent interactions are responsible for stereocontrol. We anticipate that our findings will open up new avenues for asymmetric deuteration.

| S-EPMC9343372 | 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