Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper-Catalyzed Regioselective Synthesis of (E)-β-Fluorovinyl Sulfones.

ABSTRACT: Organofluorine compounds are finding increasing application in a variety of fields such as pharmaceutical, agrochemical, and material sciences. However, given the scarcity of fluorine-containing natural products, advancement in this area depends almost entirely on the development of new synthetic methodologies. In this article, we present the synthesis of a series of previously undescribed (E)-β-fluorovinyl sulfones via a simple copper-catalyzed addition of hydrogen fluoride to alkynyl sulfone starting materials in varying yields and E/Z selectivities. The hydrogenation of these products was also explored and compared with the hydrogenation of the related Z isomers. These new products may find interesting applications, given the versatility of vinyl sulfones in chemical synthesis and the unique properties of vinyl fluorides in biological settings.

SUBMITTER: Roman R

PROVIDER: S-EPMC6514952 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copper-Catalyzed Regioselective Synthesis of (E)-β-Fluorovinyl Sulfones.

Román Raquel R Barrio Pablo P Mateu Natalia N Sedgwick Daniel M DM Fustero Santos S

Molecules (Basel, Switzerland) 20190420 8

Organofluorine compounds are finding increasing application in a variety of fields such as pharmaceutical, agrochemical, and material sciences. However, given the scarcity of fluorine-containing natural products, advancement in this area depends almost entirely on the development of new synthetic methodologies. In this article, we present the synthesis of a series of previously undescribed (E)-β-fluorovinyl sulfones via a simple copper-catalyzed addition of hydrogen fluoride to alkynyl su ...[more]

PMID: 31009999

Similar Datasets

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones.

Project description:Enantiopure (R,R) and (S,S)-dimethyl-bis(ethylenedithio)tetrathiafulvalene monosulfones have been synthesized by the aerial oxidation of the chiral dithiolates generated from the propionitrile-protected precursors. Both enantiomers crystallize in the orthorhombic chiral space group P212121. They show a boat-type conformation of the TTF moiety, a rather rigid dithiin sulfone ring and the methyl groups in a bisequatorial conformation. Cyclic voltammetry measurements indicate fully reversible oxidation in radical cation and dication species.

| S-EPMC4505188 | biostudies-literature

Copper-catalyzed regioselective ortho C-H cyanation of vinylarenes.

Project description:A copper-based catalytic technique for the regioselective ortho C-H cyanation of vinylarenes has been developed. This method provides an effective means for the selective functionalization of vinylarene derivatives. A copper-catalyzed cyanative dearomatization mechanism is proposed to account for the regiochemical course of this reaction.

| S-EPMC4127133 | biostudies-literature

Ligand-Controlled Regioselective Copper-Catalyzed Trifluoromethylation To Generate (Trifluoromethyl)allenes.

Project description:"Cu-CF3" species have been used historically for a broad spectrum of nucleophilic trifluoromethylation reactions. Although recent advancements have employed ligands to stabilize and harness the reactivity of this key organometallic intermediate, the ability of a ligand to differentiate a regiochemical outcome of a Cu-CF3-mediated or -catalyzed reaction has not been previously reported. Herein, we report the first example of a Cu-catalyzed trifluoromethylation reaction in which a ligand controls the regiochemical outcome. More specifically, we demonstrate the ability of bipyridyl-derived ligands to control the regioselectivity of the Cu-catalyzed nucleophilic trifluoromethylation reactions of propargyl electrophiles to generate (trifluoromethyl)allenes. This method provides a variety of di-, tri-, and tetrasubstituted (trifluoromethyl)allenes, which can be further modified to generate complex fluorinated substructures.

| S-EPMC4433581 | biostudies-literature

Rh(III)-catalyzed regioselective synthesis of pyridines from alkenes and α,β-unsaturated oxime esters.

Project description:α,β-Unsaturated O-pivaloyl oximes are coupled to alkenes by Rh(III) catalysis to afford substituted pyridines. The reaction with activated alkenes is exceptionally regioselective and high-yielding. Mechanistic studies suggest that heterocycle formation proceeds via reversible C-H activation, alkene insertion, and a C-N bond formation/N-O bond cleavage process.

| S-EPMC3541442 | biostudies-literature

Copper Salts/TBAB-Catalyzed Chemo- and Regioselective β-C(sp3)-H Acyloxylation of Aliphatic Amides.

Project description:An efficient Cu(II)-catalyzed and tetrabutylammonium bromide (TBAB)-promoted strategy for highly regioselective and chemoselective C(sp3)-H acyloxylation of aliphatic amides is described. Acyloxylation occurs selectively at the β position with a broad substrate scope of carboxylic acids and aliphatic amides and good functional group compatibility. Notably, the competing reaction of intramolecular dehydrogenative amidation and intermolecular acyloxylation could be efficiently controlled by the amount of copper salt and the addition of TBAB. The intramolecular dehydrogenative amidation product was obtained in high yield when the amount of copper salts was increased. However, when TBAB was used as an additive, a preference for acyloxylation over intramolecular amidation was observed and the acyloxylated products were obtained in good yield. Preliminary studies were carried out to gain insights into the mechanism.

| S-EPMC6648367 | biostudies-literature

Regioselective copper-catalyzed amination of chlorobenzoic acids: synthesis and solid-state structures of N-aryl anthranilic acid derivatives.

Project description:[reaction, structure: see text] A chemo- and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99% yield. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tert-butylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting trans-anti and unprecedented trans-syn dimeric structures.

| S-EPMC2533712 | biostudies-literature

Copper-Catalyzed Enantio-, Diastereo-, and Regioselective [2,3]-Rearrangements of Iodonium Ylides.

Project description:The first highly enantioselective, diastereoselective, and regioselective [2,3]-rearrangement of iodonium ylides has been developed as a general solution to catalytic onium ylide rearrangements. In the presence of a chiral copper catalyst, substituted allylic iodides couple with α-diazoesters to generate metal-coordinated iodonium ylides, which undergo [2,3]-rearrangements with high selectivities (up to >95:5 r.r., up to >95:5 d.r., and up to 97 % ee). The enantioenriched iodoester products can be converted stereospecifically into a variety of onium ylide rearrangement products, as well as compounds that are not accessible by classical onium ylide rearrangements.

| S-EPMC5674996 | biostudies-literature

Lewis Acid Enabled Copper-Catalyzed Asymmetric Synthesis of Chiral β-Substituted Amides.

Project description:Here we report that readily available silyl- and boron-based Lewis acids in combination with chiral copper catalysts are able to overcome the reactivity issues of unactivated enamides, known as the least reactive carboxylic acid derivatives, toward alkylation with organomagnesium reagents. Allowing unequaled chemo-reactivity and stereocontrol in catalytic asymmetric conjugate addition to enamides, the method is distinguished by its unprecedented reaction scope, allowing even the most challenging and synthetically important methylations to be accomplished with good yields and excellent enantioselectivities. This catalytic protocol tolerates a broad temperature range (-78 °C to ambient) and scale up (10 g), while the chiral catalyst can be reused without affecting overall efficiency. Mechanistic studies revealed the fate of the Lewis acid in each elementary step of the copper-catalyzed conjugate addition of Grignard reagents to enamides, allowing us to identify the most likely catalytic cycle of the reaction.

| S-EPMC5639465 | biostudies-literature

Copper-Catalyzed Alkylation of Nitroalkanes with α-Bromonitriles: Synthesis of β-Cyanonitroalkanes.

Project description:Copper catalysis now enables the efficient C-alkylation of nitroalkanes with α-bromonitriles. Using a simple and inexpensive catalyst, this process provides access to β-cyanonitroalkanes. The method is highly tolerant of various functional groups and substitution patterns. These functionally dense products serve as orthogonally masked 1,3-diamines, which can be revealed selectively for access to differentially substituted diamines. These products can also be exploited for the formation of complex cyanoalkenes and 5-aminoisoxazoles.

| S-EPMC4927086 | biostudies-literature

Enantioselective Ir-Catalyzed Hydrogenation of Terminal Homoallyl Sulfones: Total Synthesis of (-)-Curcumene.

Project description:A novel methodology for the preparation of chiral methyl benzylic compounds is reported. Terminal homoallyl sulfones were prepared from homoallyl alcohols, which are easily accessible through the recently reported Lewis acid isomerization of oxetanes. The iridium-catalyzed asymmetric hydrogenation of homoallylic sulfones afforded γ-chiral sulfones with excellent enantioselectivities (up to 98% ee). The synthetic potential of this novel methodology was demonstrated by the total synthesis of (R)-(-)-curcumene.

| S-EPMC10013179 | biostudies-literature