Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Late-stage deoxyfluorination of alcohols with PhenoFluor.

ABSTRACT: An operationally simple protocol for the selective deoxyfluorination of structurally complex alcohols is presented. Several fluorinated derivatives of natural products and pharmaceuticals have been prepared to showcase the potential of the method for late-stage diversification and its functional group compatibility. A series of simple guidelines for predicting the selectivity in substrates with multiple alcohols is given.

SUBMITTER: Sladojevich F

PROVIDER: S-EPMC3596866 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Late-stage deoxyfluorination of alcohols with PhenoFluor.

Sladojevich Filippo F Arlow Sophie I SI Tang Pingping P Ritter Tobias T

Journal of the American Chemical Society 20130211 7

An operationally simple protocol for the selective deoxyfluorination of structurally complex alcohols is presented. Several fluorinated derivatives of natural products and pharmaceuticals have been prepared to showcase the potential of the method for late-stage diversification and its functional group compatibility. A series of simple guidelines for predicting the selectivity in substrates with multiple alcohols is given. ...[more]

PMID: 23397884

Similar Datasets

Deoxyfluorination of alcohols with 3,3-difluoro-1,2-diarylcyclopropenes.

Project description:Aromatic cation activation is a useful strategy to promote deoxyfunctionalization; however, the deoxyfluorination of alcohols with cyclopropenium cation remains an unsolved problem due to the weak nucleophilicity of fluoride ion. Here we report the use of 3,3-difluoro-1,2-diarylcyclopropenes (CpFluors) as easily accessible and reactivity-tunable deoxyfluorination reagents. The electronic nature of CpFluors is critical for fluorination of monoalcohols via alkoxycyclopropenium cations, and CpFluors with electron-rich aryl substituents facilitate the transformation with high efficiency; however, selective monofluorination of 1,2- and 1,3-diols, which proceeds via cyclopropenone acetals, is less dependent on the electronic nature of CpFluors. Moreover, CpFluors are more sensitive to the electronic nature of alcohols than many other deoxyfluorination reagents, thus fluorination of longer diols can be achieved selectively at the relatively electron-rich position. This research not only unveils the first example of deoxyfluorination reagents that contain an all-carbon scaffold, but also sheds light on the divergent reactivity of cyclopropenium cation in deoxyfunctionalization of alcohols.

| S-EPMC5114535 | biostudies-literature

Photoredox-catalyzed deoxyfluorination of activated alcohols with Selectfluor<sup>®</sup>.

Project description:Herein we disclose a deoxyfluorination of alcohols with an electrophilic fluorine source via visible-light photoredox catalysis. This radical-mediated C-F coupling is capable of fluorinating secondary and tertiary alcohols efficiently, complementing previously reported nucleophilic deoxyfluorination protocols.

| S-EPMC7441851 | biostudies-literature

Late-Stage C-H Acylation of Tyrosine-Containing Oligopeptides with Alcohols.

Project description:The selective tagging of amino acids within a peptide framework while using atom-economical C-H counterparts poses an unmet challenge within peptide chemistry. Herein, we report a novel Pd-catalyzed late-stage C-H acylation of a collection of Tyr-containing peptides with alcohols. This water-compatible labeling technique is distinguished by its reliable scalability and features the use of ethanol as a renewable feedstock for the assembly of a variety of peptidomimetics.

| S-EPMC8453636 | biostudies-literature

Light-Mediated Formal Radical Deoxyfluorination of Tertiary Alcohols through Selective Single-Electron Oxidation with TEDA2+.

Project description:The synthesis of tertiary alkyl fluorides through a formal radical deoxyfluorination process is described herein. This light-mediated, catalyst-free methodology is fast and broadly applicable allowing for the preparation of C-F bonds from (hetero)benzylic, propargylic, and non-activated tertiary alcohol derivatives. Preliminary mechanistic studies support that the key step of the reaction is the single-electron oxidation of cesium oxalates-which are readily available from the corresponding tertiary alcohols-with in situ generated TEDA2+. (TEDA: N-(chloromethyl)triethylenediamine), a radical cation derived from Selectfluor®.

| S-EPMC6899844 | biostudies-literature

Deoxyfluorination of phenols.

Project description:An operationally simple ipso fluorination of phenols with a new deoxyfluorination reagent is presented.

| S-EPMC3148096 | biostudies-literature

Deoxyfluorination of Electron-Deficient Phenols.

Project description:In this study, we report a facile synthesis of 2-chloro-1,3-bis(2,6-diisopropylphenyl)imidazolium salts in aqueous media under ambient conditions using hypochlorite as a chlorinating agent. In addition, an air-stable and moisture-insensitive deoxyfluorination reagent based on poly[hydrogen fluoride] salt is presented, which is capable of converting electron-deficient phenols or aryl silyl ethers into the corresponding aryl fluorides in the presence of DBU as a base, with good to excellent yields and high tolerance to functional groups.

| S-EPMC10226106 | biostudies-literature

Enzymatic Late-Stage Modifications: Better Late Than Never.

Project description:Enzyme catalysis is gaining increasing importance in synthetic chemistry. Nowadays, the growing number of biocatalysts accessible by means of bioinformatics and enzyme engineering opens up an immense variety of selective reactions. Biocatalysis especially provides excellent opportunities for late-stage modification often superior to conventional de novo synthesis. Enzymes have proven to be useful for direct introduction of functional groups into complex scaffolds, as well as for rapid diversification of compound libraries. Particularly important and highly topical are enzyme-catalysed oxyfunctionalisations, halogenations, methylations, reductions, and amide bond formations due to the high prevalence of these motifs in pharmaceuticals. This Review gives an overview of the strengths and limitations of enzymatic late-stage modifications using native and engineered enzymes in synthesis while focusing on important examples in drug development.

| S-EPMC8359417 | biostudies-literature

NORMALvs late stage OSCC

Project description:In order to identify genes with differential gene expression or alternative splicing between the groups Normal and late stage OSCC (Stage III and IV), we study 16 hybridizations (6 normal; 10 late stage OSCC) on the HumanGene10ST array using mixed model analysis of variance. 1323 genes with significant gene expression differences between the groups and 357 genes with significant exon-group interaction (a symptom of alternative splicing) were found, including 129 genes with both gene and possible splicing differences (p<0.01). Contingency table analysis of the set of studied genes and a dataset of known pathways and gene classifications revealed that the set of alternatively spliced and expressed genes were found to be significantly over-represented in groups of the GOMolFn, GOProcess, GOCellLoc, and Pathway classes (p<0.01). Algorithm ANOVA study of 16 HumanGene10ST files.

2014-09-30 | GSE56532 | GEO

Silver-catalyzed late-stage fluorination.

Project description:Carbon-fluorine bond formation by transition metal catalysis is difficult, and only a few methods for the synthesis of aryl fluorides have been developed. All reported transition-metal-catalyzed fluorination reactions for the synthesis of functionalized arenes are based on palladium. Here we present silver catalysis for carbon-fluorine bond formation. Our report is the first example of the use of the transition metal silver to form carbon-heteroatom bonds by cross-coupling catalysis. The functional group tolerance and substrate scope presented here have not been demonstrated for any other fluorination reaction to date.

| S-EPMC2935811 | biostudies-literature

NORMALvs late stage OSCC

2014-09-30 | E-GEOD-56532 | biostudies-arrayexpress