Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Palladium-catalyzed decarboxylative rearrangements of allyl 2,2,2-trifluoroethyl malonates: direct access to homoallylic esters.

ABSTRACT: Homoallylic esters are obtained in a single transformation from allyl 2,2,2-trifluoroethyl malonates by using a Pd(0) catalyst. Facile decarboxylation of allyl 2,2,2-trifluoroethyl malonates is attributed to a decrease in pK(a) compared to allyl methyl malonates. Subsequent reduction of the homoallylic 2,2,2-trifluoroethyl ester provides a (hydroxyethyl)cyclopentenyl derivative that represents a key intermediate in the synthesis of carbocyclic nucleosides. A select allyl 2,2,2-trifluoroethyl malonate undergoes a decarboxylative Claisen rearrangement to provide a regioisomeric homoallylic ester.

SUBMITTER: Tardibono LP

PROVIDER: S-EPMC2767373 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Palladium-catalyzed decarboxylative rearrangements of allyl 2,2,2-trifluoroethyl malonates: direct access to homoallylic esters.

Tardibono Lawrence P LP Patzner Jerod J Cesario Cara C Miller Marvin J MJ

Organic letters 20090901 18

Homoallylic esters are obtained in a single transformation from allyl 2,2,2-trifluoroethyl malonates by using a Pd(0) catalyst. Facile decarboxylation of allyl 2,2,2-trifluoroethyl malonates is attributed to a decrease in pK(a) compared to allyl methyl malonates. Subsequent reduction of the homoallylic 2,2,2-trifluoroethyl ester provides a (hydroxyethyl)cyclopentenyl derivative that represents a key intermediate in the synthesis of carbocyclic nucleosides. A select allyl 2,2,2-trifluoroethyl mal ...[more]

PMID: 19694457

Similar Datasets

Palladium-catalyzed decarboxylative sp3-sp3 coupling of nitrobenzene acetic esters.

Project description:Allylic esters of nitrobenzene acetic acids undergo facile palladium-catalyzed decarboxylative coupling. Both mono- and dinitroarene substrates give high yields of the coupled products. Moreover, the rates of the reactions suggest that decarboxylation is rate-limiting and substrates that sterically disfavor attainment of the reactive conformation for decarboxylation are not viable. Finally, reduction of the product nitroarenes to the corresponding anilines provides access to a variety of heterocycles including quinolines and dihydroquinolones.

| S-EPMC2707754 | biostudies-literature

Enzymatic enantioselective decarboxylative protonation of heteroaryl malonates.

Project description:The enzyme aryl/alkenyl malonate decarboxylase (AMDase) catalyses the enantioselective decarboxylative protonation (EDP) of a range of disubstituted malonic acids to give homochiral carboxylic acids that are valuable synthetic intermediates. AMDase exhibits a number of advantages over the non-enzymatic EDP methods developed to date including higher enantioselectivity and more environmentally benign reaction conditions. In this report, AMDase and engineered variants have been used to produce a range of enantioenriched heteroaromatic ?-hydroxycarboxylic acids, including pharmaceutical precursors, from readily accessible ?-hydroxymalonates. The enzymatic method described here represents an improvement upon existing synthetic chemistry methods that have been used to produce similar compounds. The relationship between the structural features of these new substrates and the kinetics associated with their enzymatic decarboxylation is explored, which offers further insight into the mechanism of AMDase.

| S-EPMC4517146 | biostudies-literature

Ligand-controlled regiodivergent palladium-catalyzed decarboxylative allylation reaction to access ?,?-difluoroketones.

Project description:?,?-Difluoroketones possess unique physicochemical properties that are useful for developing therapeutics and probes for chemical biology. To access the ?-allyl-?,?-difluoroketone substructure, complementary palladium-catalyzed decarboxylative allylation reactions were developed to provide linear and branched ?-allyl-?,?-difluoroketones. For these orthogonal processes, the fluorination pattern of the substrate enabled the ligands to dictate the regioselectivity of the transformations.

| S-EPMC4373536 | biostudies-literature

Visible-Light-Mediated Decarboxylative Radical Additions to Vinyl Boronic Esters: Rapid Access to ?-Amino Boronic Esters.

Project description:The synthesis of alkyl boronic esters by direct decarboxylative radical addition of carboxylic acids to vinyl boronic esters is described. The reaction proceeds under mild photoredox catalysis and involves an unprecedented single-electron reduction of an ?-boryl radical intermediate to the corresponding anion. The reaction is amenable to a diverse range of substrates, including ?-amino, ?-oxy, and alkyl carboxylic acids, thus providing a novel method to rapidly access boron-containing molecules of potential biological importance.

| S-EPMC5838549 | biostudies-literature

A convenient enantioselective decarboxylative aldol reaction to access chiral ?-hydroxy esters using ?-keto acids.

Project description:We show a convenient decarboxylative aldol process using a scandium catalyst and a PYBOX ligand to generate a series of highly functionalized chiral ?-hydroxy esters. The protocol tolerates a broad range of ?-keto acids with inactivated aromatic and aliphatic ?-keto esters. The possible mechanism is rationalized.

| S-EPMC4077541 | biostudies-literature

Palladium-catalyzed hydroarylation of 1,3-dienes with boronic esters via reductive formation of pi-allyl palladium intermediates under oxidative conditions.

Project description:A palladium-catalyzed reductive cross-coupling of 1,3-dienes with boronic esters in which a pi-allyl Pd species is generated directly from a 1,3-diene via a Pd-catalyzed aerobic alcohol oxidation is reported. Both the scope of the process and the origin of a highly selective 1,2-addition are discussed.

| S-EPMC2911521 | biostudies-literature

An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

Project description:A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

| S-EPMC3426664 | biostudies-literature

Conjugate addition/Ireland-Claisen rearrangements of allyl fumarates: simple access to terminally differentiated succinates.

Project description:The conjugate addition of dialkylzinc reagents to allyl fumarates with subsequent Ireland-Claisen rearrangement has been accomplished yielding substituted unsymmetrical succinic acid derivatives. This one-pot reaction creates two new carbon-carbon bonds at contiguous stereogenic centers. The reaction proceeds for several alkylzinc reagents and substituted allyl fumarates. The products contain distinguishable functional handles for further manipulation.

| S-EPMC2822989 | biostudies-literature

2,2,2-Trifluoroethyl 6-thio-?-D-glucopyranoside as a selective tag for cysteines in proteins.

Project description:A synthetic route to a trifluoromethyl and thiol containing glucose derivative (2,2,2-trifluoroethyl 6-thio-?-D-glucopyranoside) is presented, which is based on microwave-assisted Fischer glycosylation under increased pressure. This water-soluble, neutral thiol-compound can be used to selectively introduce a fluorine probe for (19)F NMR spectroscopy on cysteines in proteins. It can be attached under mild conditions in an aqueous environment without the risk of denaturing the protein. This tag has been applied to determine the redox-state of two cysteine residues in a bacterial transcription activator. Qualitative information about the solvent accessibility can be obtained from F-19 solvent PREs.

| S-EPMC4067056 | biostudies-literature

Traversing Steric Limitations by Cooperative Lewis Base/Palladium Catalysis: An Enantioselective Synthesis of ?-Branched Esters Using 2-Substituted Allyl Electrophiles.

Project description:Cooperative catalysis enables the direct enantioselective ?-allylation of linear prochiral esters with 2-substituted allyl electrophiles. Critical to the successful development of the method was the recognition that metal-centered reactivity and the source of enantiocontrol are independent. This feature is unique to simultaneous catalysis events and permits logical tuning of the supporting ligands without compromising enantioselectivity.

| S-EPMC6038818 | 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