Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Unstrained C-C bond activation and directed fluorination through photocatalytically-generated radical cations.

ABSTRACT: Expanding the repertoire of controlled radical fluorination techniques, we present a photosensitized unstrained C-C bond activation/directed monofluorination method using Selectfluor and 9-fluorenone. The reaction is amenable to the opening of multiple 1-acetal-2-aryl substituted rings to yield ?-fluoro carboxylic acids, esters, alcohols, and ketones with relative ease. Initial mechanistic insight suggests radical ion intermediates.

SUBMITTER: Pitts CR

PROVIDER: S-EPMC5669245 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Unstrained C-C bond activation and directed fluorination through photocatalytically-generated radical cations.

Pitts Cody Ross CR Bloom Michelle Sheanne MS Bume Desta Doro DD Zhang Qinze Arthur QA Lectka Thomas T

Chemical science 20150623 9

Expanding the repertoire of controlled radical fluorination techniques, we present a photosensitized unstrained C-C bond activation/directed monofluorination method using Selectfluor and 9-fluorenone. The reaction is amenable to the opening of multiple 1-acetal-2-aryl substituted rings to yield ω-fluoro carboxylic acids, esters, alcohols, and ketones with relative ease. Initial mechanistic insight suggests radical ion intermediates. ...[more]

PMID: 29449927

Similar Datasets

Novel C?-C? bond cleavages of tryptophan-containing peptide radical cations.

Project description:In this study, we observed unprecedented cleavages of the C(?)-C(?) bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M(•+)) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density functional theory (DFT) calculations to study the mechanism of this bond cleavage, which forms [M - 116](+) ions. The formation of an ?-carbon radical intermediate at the tryptophan residue for the subsequent C(?)-C(?) bond cleavage is analogous to that occurring at leucine residues, producing the same product ions; this hypothesis was supported by the identical product ion spectra of [LGGGH - 43](+) and [WGGGH - 116](+), obtained from the CID of [LGGGH](•+) and [WGGGH](•+), respectively. Elimination of the neutral 116-Da radical requires inevitable dehydrogenation of the indole nitrogen atom, leaving the radical centered formally on the indole nitrogen atom ([Ind](•)-2), in agreement with the CID data for [WGGGH](•+) and [W(1-CH3)GGGH](•+); replacing the tryptophan residue with a 1-methyltryptophan residue results in a change of the base peak from that arising from a neutral radical loss (116 Da) to that arising from a molecule loss (131 Da), both originating from C(?)-C(?) bond cleavage. Hydrogen atom transfer or proton transfer to the ?-carbon atom of the tryptophan residue weakens the C(?)-C(?) bond and, therefore, decreases the dissociation energy barrier dramatically.

| S-EPMC3264861 | biostudies-literature

Intramolecular Acetyl Transfer to Olefins by Catalytic C-C Bond Activation of Unstrained Ketones.

Project description:A rhodium-catalyzed intramolecular acetyl-group transfer has been achieved through a "cut and sew" process. The challenge arises from the existence of different competitive pathways. Preliminary success has been achieved with unstrained enones that contain a biaryl linker. The use of an electron-rich N-heterocycilc carbene (NHC) ligand is effective to inhibit undesired ?-hydrogen elimination. Various 9,10-dihydrophenanthrene derivatives can be prepared with excellent functional-group compatibility. The 13 C-labelling study suggests that the reaction begins with cleavage of the unstrained C-C bond, followed by migratory insertion and reductive elimination.

| S-EPMC5798000 | biostudies-literature

Hydroxy-directed fluorination of remote unactivated C(sp<sup>3</sup>)-H bonds: a new age of diastereoselective radical fluorination.

Project description:We report a photochemically induced, hydroxy-directed fluorination that addresses the prevailing challenge of high diastereoselectivity in this burgeoning field. Numerous simple and complex motifs showcase a spectrum of regio- and stereochemical outcomes based on the configuration of the hydroxy group. Notable examples include a long-sought switch in the selectivity of the refractory sclareolide core, an override of benzylic fluorination, and a rare case of 3,3'-difluorination. Furthermore, calculations illuminate a low barrier transition state for fluorination, supporting our notion that alcohols are engaged in coordinated reagent direction. A hydrogen bonding interaction between the innate hydroxy directing group and fluorine is also highlighted for several substrates with 19F-1H HOESY experiments, calculations, and more.

| S-EPMC9200124 | biostudies-literature

Diaryldichalcogenide radical cations.

Project description:One-electron oxidation of two series of diaryldichalcogenides (C6F5E)2 (13a-c) and (2,6-Mes2C6H3E)2 (16a-c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF5 and SbF5 gave rise to the formation of thermally unstable radical cations [(C6F5S)2]˙+ (14a) and [(C6F5Se)2]˙+ (14b) that were isolated as [Sb2F11]- and [As2F11]- salts, respectively. The reaction of 13c with AsF5 afforded only the product of a Te-C bond cleavage, namely the previously known dication [Te4]2+ that was isolated as [AsF6]- salt. The reaction of (2,6-Mes2C6H3E)2 (16a-c) with [NO][SbF6] provided the corresponding radical cations [(2,6-Mes2C6H3E)2]˙+ (17a-c; E = S, Se, Te) in the form of thermally stable [SbF6]- salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.

| S-EPMC5588450 | biostudies-literature

Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol.

Project description:Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon-hydrogen bond cleavage.

| S-EPMC3728896 | biostudies-literature

Adenovirus inactivation by in situ photocatalytically and photoelectrocatalytically generated halogen viricides.

Project description:This study investigates and compares the virucidal performances of photocatalytic (PC) and photoelectrocatalytic (PEC) treatments in the presence and absence of halides, such as Br- and Cl-, under comparable experimental conditions. The results confirm that the PC virucidal efficiency can be enhanced in the presence of low halide concentrations (e.g., X = Br- or Cl-) and further enhanced by applying potential bias onto the photoanode in a PEC system. The PEC treatment in the presence of 1.0 mM Br (PEC-Br) shows the highest virucidal efficiency, enabling complete inactivation of a ∼1000 TCID50 replication-deficient recombinant adenovirus (RDRADS) population within 31.7 s. The superior virucidal performances of PEC-X treatments can be attributed to the increased production of active oxygen species and additional viricides resulting from the PEC halide oxidation, as well as prolonged lifetime of photoholes (h+ ) for direct inactivation. The findings of this work confirm that new forms of active species generated in situ via a PC or PEC process are effective for viruses.

| S-EPMC7108339 | biostudies-literature

Sila-spirocyclization involving unstrained C(sp<sup>3</sup>)-Si bond cleavage.

Project description:C - Si Bond cleavage is one of the key elemental steps for a wide variety of silicon-based transformations. However, the cleavage of unstrained Si-C(sp3) bonds catalyzed by transition metal are still in their infancy. They generally involve the insertion of a M - C(sp2) species into the C - Si bond and consequent intramolecular C(sp2)‒Si coupling to exclusively produce siloles. Here we report the Pd-catalyzed sila-spirocyclization, in which the Si-C(sp3) bond is activated by the insertion of a M - C(sp3) species and followed by the formation of a new C(sp3)‒Si bond, allowing the construction of diverse spirosilacycles. This reactivity mode, which is strongly supported by DFT calculations may open an avenue for the Si-C(sp3) bond cleavage and silacycle synthesis.

| S-EPMC9637223 | biostudies-literature

Pd-Catalyzed Directed Thiocyanation Reaction by C-H Bond Activation.

Project description:The Pd-catalyzed directed thiocyanation reaction of arenes and heteroarenes by C-H bond activation was achieved. In the presence of an electrophilic SCN source, this original methodology offered an efficient tool to access a panel of functionalized thiocyanated compounds (21 examples, up to 78 % yield). Post-functionalization reactions further demonstrated the synthetic utility of the approach by converting the SCN-containing molecules into value-added scaffolds.

| S-EPMC7756308 | biostudies-literature

H-Bond donor parameters for cations.

Project description:UV/Vis absorption and NMR spectroscopy titrations have been used to investigate the formation of complexes between cations and neutral H-bond acceptors in organic solvents. Complexes formed by two different H-bond acceptors with fifteen different cations were studied in acetone and in acetonitrile. The effects of water and ion pairing with the counter-anion were found to be negligible in the two polar solvents employed for this study. The data were used to determine self-consistent H-bond donor parameters (α) for a series of organic and inorganic cations; guanidinium, primary, tertiary and quaternary ammonium, imidazolium, methylpyridinium, lithium, sodium, potassium, rubidium and caesium. The results demonstrate the transferability of α parameters for cations between different solvents and different H-bond acceptor partners, allowing reliable prediction of cation recognition properties in different environments. Lithium and protonated nitrogen cations form the most stable complexes, but the α parameter is only 5.0, which is similar to the neutral H-bond donor 3-trifluoromethyl,4-nitrophenol (α = 5.1). Quaternary ammonium is the weakest H-bond donor investigated with an α value of 2.7, which is comparable to an alcohol. The α parameters for alkali metal cations decrease down the group from 5.0 (Li+) to 3.5 (Cs+).

| S-EPMC6566073 | biostudies-literature

Crystalline boron-linked tetraaminoethylene radical cations.

Project description:Single-electron oxidation of neutral boryl-linked tetraaminoethylene derivatives 4 led to the formation of radical cations 4?+ , which have been isolated and fully characterized. X-ray diffraction analysis, EPR spectroscopy, and computational studies revealed that the unpaired electron is delocalized over the B2N4C2 skeleton and the spin density mainly resides on the carbon and boron atoms.

| S-EPMC5674142 | 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