Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Palladium-catalysed alkene chain-running isomerization.

ABSTRACT: We report a method for palladium-catalysed chain-running isomerization of terminal and internal alkenes. Using an air-stable 2,9-dimethylphenanthroline-palladium catalyst in combination with NaBAr4 promoter, olefins are converted to the most stable double bond isomer at -30 to 20 °C. Silyl enol ethers are readily formed from silylated allylic alcohols. Fluorinated substituents are compatible with the reaction conditions, allowing the synthesis of fluoroenolates. Catalyst loading as low as 0.05% can be employed on a gram scale.

SUBMITTER: Kocen AL

PROVIDER: S-EPMC5705238 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Palladium-catalysed alkene chain-running isomerization.

Kocen Andrew L AL Brookhart Maurice M Daugulis Olafs O

Chemical communications (Cambridge, England) 20170901 72

We report a method for palladium-catalysed chain-running isomerization of terminal and internal alkenes. Using an air-stable 2,9-dimethylphenanthroline-palladium catalyst in combination with NaBAr<sub>4</sub> promoter, olefins are converted to the most stable double bond isomer at -30 to 20 °C. Silyl enol ethers are readily formed from silylated allylic alcohols. Fluorinated substituents are compatible with the reaction conditions, allowing the synthesis of fluoroenolates. Catalyst loading as lo ...[more]

PMID: 28835962

Similar Datasets

Olefin Functionalization/Isomerization Enables Stereoselective Alkene Synthesis.

Project description:Despite tremendous efforts aimed at devising methods for stereoselective alkene synthesis, critical challenges are yet to be addressed. Direct access to a diverse range of 1aryl(boryl)-1-methyl-functionalized tri- and tetrasubstituted trans alkenes, entities that are prevalent in many important molecules of interest, through a catalytic manifold from readily available α-olefin substrates remains elusive. Here, we demonstrate that catalytic amounts of a nonprecious N-heterocyclic carbene-Ni(I) complex in conjunction with a sterically bulky base promote site- and trans-selective union of monosubstituted olefins with a wide array of electrophilic reagents to deliver tri- and tetrasubstituted alkenes in up to 92% yield and >98% regio- and stereoselectivity. The protocol is amenable to the preparation of carbon- and heteroatom-substituted C=C bonds, providing distinct advantages over existing transformations. Utility is highlighted through concise stereoselective synthesis of biologically active compounds.

| S-EPMC9431960 | biostudies-literature

Alkene Isomerization Revitalizes the Coates-Claisen Rearrangement.

Project description:The [3,3]-sigmatropic rearrangement of allylic vinyl acetals, first investigated by Coates nearly four decades ago, is set apart from other variants of the Claisen rearrangement owing to the versatile monoprotected 1,5-dicarbonyl motif featured in the products. Unfortunately, the synthetically elusive nature of the substrates has thus far precluded the widespread application of this attractive transformation. Herein, we show that the key allylic vinyl acetals can be efficiently generated through alkene isomerization of their readily available regioisomeric counterparts (derived from allylic alcohols and α,β-unsaturated aldehydes), thus enabling the first systematic study of the substrate scope of this rearrangement, as well as the discovery of exceptionally mild conditions for its mediation by Lewis and Brønsted acids.

| S-EPMC8456971 | biostudies-literature

Stereodivergent Access to Trisubstituted Alkenylboronate Esters through Alkene Isomerization.

Project description:We report an efficient method for the preparation of synthetically valuable trisubstituted alkenylboronate esters through alkene isomerization of their readily available 1,1-disubstituted regioisomeric counterparts. Either stereoisomer of the target alkenylboronate motif can be obtained at will from the same starting material by employing different isomerization catalysts.

| S-EPMC8650100 | biostudies-literature

Palladium-catalysed anti-Markovnikov selective oxidative amination.

Project description:In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to a reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a palladium-catalysed oxidative amination reaction in which the addition of the nitrogen occurs at the less-substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.

| S-EPMC6092016 | biostudies-literature

Palladium-catalysed synthesis of triaryl(heteroaryl)methanes.

Project description:Tetraarylmethane derivatives are desirable for a variety of applications, but difficult to access with modern C-C bond-forming reactions. Here we report a straightforward method for palladium-catalysed arylation of aryl(heteroaryl)methanes and diaryl(heteroaryl)methanes with aryl chlorides. This reaction enables introduction of various aryl groups to construct triaryl(heteroaryl)methanes via a C-H functionalization in good to excellent yield, and represents the first step towards a general transition metal catalysed synthesis of tetraarylmethanes.

| S-EPMC5355892 | biostudies-literature

Asymmetric remote C-H borylation of internal alkenes via alkene isomerization.

Project description:Recent years have witnessed the growing interest in the remote functionalization of alkenes for it offers a strategy to activate the challenging C-H bonds distant from the initiation point via alkene isomerization/functionalization. However, the catalytic enantioselective isomerization/functionalization with one single transition metal catalyst remains rare. Here we report a highly regio- and enantioselective cobalt-catalyzed remote C-H bond borylation of internal alkenes via sequential alkene isomerization/hydroboration. A chiral ligand featured twisted pincer, anionic, and non-rigid characters is designed and used for this transformation. This methodology, which is operationally simple using low catalyst loading without additional activator, shows excellent enantioselectivity and can be used to convert various internal alkenes with regio- and stereoisomers to valuable chiral secondary organoboronates with good functional group tolerance.

| S-EPMC6158179 | biostudies-literature

Palladium-Catalyzed Alkene Carboamination Reactions of Electron-Poor Nitrogen Nucleophiles.

Project description:Modified reaction conditions that facilitate Pd-catalyzed alkene carboamination reactions of electron-deficient nitrogen nucleophiles are reported. Pent-4-enylamine derivatives bearing N-tosyl or N-trifluoroacetyl groups are coupled with aryl triflates to afford substituted pyrrolidines in good yield. These reactions proceed via a mechanism involving anti-aminopalladation of the alkene, which differs from previously reported analogous reactions of N-aryl and N-boc pentenylamines. The application of these conditions to a formal synthesis of (±)-aphanorphine is also described.

| S-EPMC4662568 | biostudies-literature

Palladium-catalysed transannular C-H functionalization of alicyclic amines.

Project description:Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

| S-EPMC5082708 | biostudies-literature

Long-Range Olefin Isomerization Catalyzed by Palladium(0) Nanoparticles.

Project description:Long-range olefin isomerization of 2-alkenylbenzoic acid derivatives going through two to five sp3-carbon atoms to give (E)-alkenes was achieved with palladium(0) nanoparticles. The substrate scope of this reaction includes carboxylic acid, ester, and primary to tertiary amides and tolerates various substituents on the benzene ring. This isomerization reaction was catalyzed by recyclable Pd(0) nanoparticles, prepared in situ from PdCl2 and characterized by X-ray powder diffraction and scanning electron microscopy analyses. 1H NMR studies and kinetic modeling supported a stepwise process. This new process was applied to synthesize a natural dihydroisocoumarin with good efficiency.

| S-EPMC6640945 | biostudies-literature

Leveraging the n→π* Interaction in Alkene Isomerization by Selective Energy Transfer Catalysis.

Project description:Examples of geometric alkene isomerization in nature are often limited to the net exergonic direction (ΔG°<0), with the antipodal net endergonic processes (ΔG°>0) comparatively under-represented. Inspired by the expansiveness of the maleate to fumarate (Z→E) isomerization in biochemistry, we investigated the inverse E→Z variant to validate nO →πC=O * interactions as a driving force for contra-thermodynamic isomerization. A general protocol involving selective energy transfer catalysis with inexpensive thioxanthone as a sensitizer (λmax =402 nm) is disclosed. Whilst in the enzymatic process nO →πC=O * interactions commonly manifest themselves in the substrate, these same interactions are shown to underpin directionality in the antipodal reaction by shortening the product alkene chromophore. The process was validated with diverse fumarate derivatives (>30 examples, up to Z:E>99:1), including the first examples of tetrasubstituted alkenes, and the involvement of nO →πC=O * interactions was confirmed by X-ray crystallography.

| S-EPMC9299456 | 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