Browse
Submit Data
Databases
API
Help

Dataset Information

18 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids.

ABSTRACT: As a key element in the construction of complex organic scaffolds, the formation of C-C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single-electron chemistry have enabled new methods for the formation of various C-C bonds. Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical-radical coupling was made possible merging N-heterocyclic carbene (NHC) and photoredox catalysis. The utility of this protocol in synthesis was showcased in the late-stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies.

SUBMITTER: Davies AV

PROVIDER: S-EPMC7250732 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis.

Project description:The direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides has been achieved via visible light-promoted photoredox catalysis. This operationally simple, redox-neutral fluorination method is amenable to a wide variety of carboxylic acids. Photon-induced oxidation of carboxylates leads to the formation of carboxyl radicals, which upon rapid CO2-extrusion and F(•) transfer from a fluorinating reagent yield the desired fluoroalkanes with high efficiency. Experimental evidence indicates that an oxidative quenching pathway is operable in this broadly applicable fluorination protocol.

| S-EPMC4862610 | biostudies-literature

Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo Acids.

Project description:The direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners. This mild decarboxylative arylation can also be utilized to efficiently access medicinal agents, as demonstrated by the rapid synthesis of fenofibrate.

| S-EPMC4526169 | biostudies-literature

Acyl Radicals from Aromatic Carboxylic Acids by Means of Visible-Light Photoredox Catalysis.

Project description:Simple and abundant carboxylic acids have been used as acyl radical precursor by means of visible-light photoredox catalysis. By the transient generation of a reactive anhydride intermediate, this redox-neutral approach offers a mild and rapid entry to high-value heterocyclic compounds without the need of UV irradiation, high temperature, high CO pressure, tin reagents, or peroxides.

| S-EPMC4648026 | biostudies-literature

Merging photoredox and nickel catalysis: decarboxylative cross-coupling of carboxylic acids with vinyl halides.

Project description:Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of ?-oxy and ?-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions.

| S-EPMC4308738 | biostudies-literature

Cooperative NHC and Photoredox Catalysis for the Synthesis of β-Trifluoromethylated Alkyl Aryl Ketones.

Project description:Despite the great potential of radical chemistry in organic synthesis, N-heterocyclic carbene (NHC)-catalyzed reactions involving radical intermediates are not well explored. This communication reports the three-component coupling of aroyl fluorides, styrenes and the Langlois reagent (CF3 SO2 Na) to give various β-trifluoromethylated alkyl aryl ketones with good functional group tolerance in moderate to high yields by cooperative photoredox/NHC catalysis. The alkene acyltrifluoromethylation proceeds via radical/radical cross coupling of ketyl radicals with benzylic C-radicals. The ketyl radicals are generated via SET reduction of in situ formed acylazolium ions whereas the benzylic radicals derive from trifluoromethyl radical addition onto styrenes.

| S-EPMC7693039 | biostudies-literature

Direct Conversion of Carboxylic Acids to Alkyl Ketones.

Project description:An efficient and mild method for acyl-Csp3 bond formation based on the direct conversion of carboxylic acids has been established. This protocol is enabled by the synergistic, Ir-photoredox/nickel catalytic cross-coupling of in situ activated carboxylic acids and alkyltrifluoroborates. This versatile method is amenable to the cross-coupling of structurally diverse carboxylic acids with various potassium alkyltrifluoroborates, affording the corresponding ketones with high yields. In this operationally simple cross-coupling protocol, aliphatic ketones are obtained in one step from bench stable, readily available carboxylic acids.

| S-EPMC5505169 | biostudies-literature

A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes.

Project description:The construction of an aryl ketone structural unit by means of catalytic carbon-carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved the direct deoxygenative ketone synthesis in aqueous solution from readily available aromatic carboxylic acids and alkenes, affording structurally diverse ketones in moderate to good yields. Visible-light photoredox catalysis enables the direct deoxygenation of acids as acyl sources with triphenylphosphine and represents a distinct perspective on activation. The synthetic robustness is supported by the late-stage modification of several pharmaceutical compounds and complex molecules. This ketone synthetic strategy is further applied to the synthesis of the drug zolpidem in three steps with 50% total yield and a concise construction of cyclophane-braced 18-20 membered macrocycloketones. It represents not only the advancement for the streamlined synthesis of aromatic ketones from feedstock chemicals, but also a photoredox radical activation mode beyond the redox potential of carboxylic acids.

| S-EPMC6115474 | biostudies-literature

(CF3CO)2O/CF3SO3H-mediated synthesis of 1,3-diketones from carboxylic acids and aromatic ketones.

Project description:A very simple and convenient reaction for 1,3-diketone preparation from carboxylic acids and aromatic ketones in TFAA/TfOH system is described. When the ?-phenylpropionic acids were used as starting materials, they initially gave 1-indanones and then underwent further acylation with the formation of 2-(?-phenylpropionyl)-1-indanones as the main reaction products. In addition, the application of the proposed protocol allowed for the synthesis of selected polysubstituted pyrazoles in a one-pot procedure directly from acids and ketones.

| S-EPMC4187061 | biostudies-literature

Room temperature decarboxylative cyanation of carboxylic acids using photoredox catalysis and cyanobenziodoxolones: a divergent mechanism compared to alkynylation.

Project description:The one-step conversion of aliphatic carboxylic acids to the corresponding nitriles has been accomplished via the merger of visible light mediated photoredox and cyanobenziodoxolones (CBX) reagents. The reaction proceeded in high yields with natural and non-natural ?-amino and ?-oxy acids, affording a broad scope of nitriles with excellent tolerance of the substituents in the ? position. The direct cyanation of dipeptides and drug precursors was also achieved. The mechanism of the decarboxylative cyanation was investigated both computationally and experimentally and compared with the previously developed alkynylation reaction. Alkynylation was found to favor direct radical addition, whereas further oxidation by CBX to a carbocation and cyanide addition appeared more favorable for cyanation. A concerted mechanism is proposed for the reaction of radicals with EBX reagents, in contrast to the usually assumed addition elimination process.

| S-EPMC5396527 | biostudies-literature

Nickel-Catalyzed Synthesis of Dialkyl Ketones from the Coupling of N-Alkyl Pyridinium Salts with Activated Carboxylic Acids.

Project description:While ketones are among the most versatile functional groups, their synthesis remains reliant upon reactive and low-abundance starting materials. In contrast, amide formation is the most-used bond-construction method in medicinal chemistry because the chemistry is reliable and draws upon large and diverse substrate pools. A new method for the synthesis of ketones is presented here that draws from the same substrates used for amide bond synthesis: amines and carboxylic acids. A nickel terpyridine catalyst couples N-alkyl pyridinium salts with in situ formed carboxylic acid fluorides or 2-pyridyl esters under reducing conditions (Mn metal). The reaction has a broad scope, as demonstrated by the synthesis of 35 different ketones bearing a wide variety of functional groups with an average yield of 60±16 %. This approach is capable of coupling diverse substrates, including pharmaceutical intermediates, to rapidly form complex ketones.

| S-EPMC7397811 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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