Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Pd-Catalyzed 1,3-Alkenylarylation of Skipped Diene via Metal Migration.

ABSTRACT: We disclose a palladium-catalyzed difunctionalization of skipped diene with alkenyl triflates and arylboronic acids to produce 1,3-alkenylarylated products. The reaction proceeded efficiently with Pd(acac)₂ as a catalyst and CsF as a base for a wide range of electron-deficient and electron-rich arylboronic acids as well as oxygen-heterocyclic, sterically hindered, and complex natural product-derived alkenyl triflates bearing various functional groups. The reaction produced 3-aryl-5-alkenylcyclohexene derivatives with 1,3-syn-disubstituted stereochemistry.

SUBMITTER: Chesley LJ

PROVIDER: S-EPMC10249098 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Pd-Catalyzed 1,3-Alkenylarylation of Skipped Diene via Metal Migration.

Chesley Lucas J LJ Poudel Dhruba P DP Sapkota Rishi R RR Dhungana Roshan K RK Lakomy Margaret G MG Giri Ramesh R

ACS omega 20230525 22

We disclose a palladium-catalyzed difunctionalization of skipped diene with alkenyl triflates and arylboronic acids to produce 1,3-alkenylarylated products. The reaction proceeded efficiently with Pd(acac)<sub>2</sub> as a catalyst and CsF as a base for a wide range of electron-deficient and electron-rich arylboronic acids as well as oxygen-heterocyclic, sterically hindered, and complex natural product-derived alkenyl triflates bearing various functional groups. The reaction produced 3-aryl-5-al ...[more]

PMID: 37305246

Similar Datasets

Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

Project description:A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

| S-EPMC4490833 | biostudies-literature

Formal Asymmetric Hydrobromination of Styrenes <i>via</i> Copper-Catalyzed 1,3-Halogen Migration.

Project description:An enantioselective Cu(I)-catalyzed 1,3-halogen migration reaction accomplishes a formal hydrobromination by transferring a bromine activating group from a sp2 carbon to a benzylic carbon in good er and with concomitant borylation of the Ar-Br bond. Computational modelling aids in understanding the reaction outcome and suggests future directions to improve the formal asymmetric hydrobromination. The benzyl bromide can be displaced with a variety of nucleophiles to produce a wide array of functionalized products.

| S-EPMC4494760 | biostudies-literature

A metal π-Lewis base activation model for Pd-catalyzed hydroamination of amines and 1,3-dienes.

Project description:As a general mechanism proposal, a Pd(ii)-H migration insertion process is not able to well explicate the Pd-catalyzed hydroamination of amines and 1,3-dienes. Here we demonstrate that 1,3-dienes form electron-neutral and HOMO-raised η2-complexes with Pd(0) via π-Lewis base activation, which undergoes protonation with a variety of acidic sources, such as Brønsted acids, Lewis acid-activated indazoles, and Pd(ii) pre-catalyst triggered ammonium salts. The resultant π-allyl palladium complexes undergo the amination reaction to give the final observed products. FMO and NPA analyses have revealed the nature of Pd(0) mediated π-Lewis base activation of 1,3-dienes. The calculation results show that the π-Lewis base activation pathway is more favourable than the Pd(ii)-H species involved one in different reactions. Further control experiments corroborated our mechanistic proposal, and an efficient Pd(0) mediated hydroamination reaction was developed.

| S-EPMC10155909 | biostudies-literature

Rh-Catalyzed rearrangement of vinylcyclopropane to 1,3-diene units attached to N-heterocycles.

Project description:Dienes embedded in quinolizidine and indolizidine structures can be prepared in four steps from cyclic nitrones and bicyclopropylidene. The key intermediates α-spirocyclopropanated N-heterocyclic ketones, generated via a domino 1,3-dipolar cycloaddition/thermal rearrangement sequence, were converted by Wittig methylenation to the corresponding vinylcyclopropanes (VCPs), which underwent rearrangement to 1,3-dienes in the presence of the Wilkinson Rh(I) complex under microwave heating. The previously unexplored Rh(I)-catalyzed opening of the VCP moiety embedded in an azapolycyclic system occurs at high temperature (110-130 °C) to afford the corresponding 1,3-dienes in moderate yield (34-53%).

| S-EPMC3063054 | biostudies-literature

Pd-Catalyzed Regioselective Cyclopropanation of 2-Substituted 1,3-Dienes

Project description: Not available

| S-EPMC10557126 | biostudies-literature

Pd-Senphos Catalyzed trans-Selective Cyanoboration of 1,3-Enynes.

Project description:The first trans-selective cyanoboration reaction of an alkyne, specifically a 1,3-enyne, is described. The reported palladium-catalyzed cyanoboration of 1,3-enynes is site-, regio-, and diastereoselective, and is uniquely enabled by the 1,4-azaborine-based Senphos ligand structure. Tetra-substituted alkenyl nitriles are obtained providing useful boron-dienenitrile building blocks that can be further functionalized. The utility of our method has been demonstrated with the synthesis of Satigrel, an anti-platelet aggregating agent.

| S-EPMC7491284 | biostudies-literature

Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3-Diene Pronucleophiles.

Project description:Recently, CuH-catalyzed reductive coupling processes involving carbonyl compounds and imines have become attractive alternatives to traditional methods for stereoselective addition because of their ability to use readily accessible and stable olefins as surrogates for organometallic nucleophiles. However, the inability to use aldehydes, which usually reduce too rapidly in the presence of copper hydride complexes to be viable substrates, has been a major limitation. Shown here is that by exploiting relative concentration effects through kinetic control, this intrinsic reactivity can be inverted and the reductive coupling of 1,3-dienes with aldehydes achieved. Using this method, both aromatic and aliphatic aldehydes can be transformed into synthetically valuable homoallylic alcohols with high levels of diastereo- and enantioselectivities, and in the presence of many useful functional groups. Furthermore, using a combination of theoretical (DFT) and experimental methods, important mechanistic features of this reaction related to stereo- and chemoselectivities were uncovered.

| S-EPMC6848771 | biostudies-literature

Formation of Transient Anionic Metal Clusters in Palladium/Diene-Catalyzed Cross-Coupling Reactions.

Project description:Despite their considerable practical value, palladium/1,3-diene-catalyzed cross-coupling reactions between Grignard reagents RMgCl and alkyl halides AlkylX remain mechanistically poorly understood. Herein, we probe the intermediates formed in these reactions by a combination of electrospray-ionization mass spectrometry, UV/Vis spectroscopy, and NMR spectroscopy. According to our results and in line with previous hypotheses, the first step of the catalytic cycle brings about transmetalation to afford organopalladate anions. These organopalladate anions apparently undergo SN 2-type reactions with the AlkylX coupling partner. The resulting neutral complexes then release the cross-coupling products by reductive elimination. In gas-phase fragmentation experiments, the occurrence of reductive eliminations was observed for anionic analogues of the neutral complexes. Although the actual catalytic cycle is supposed to involve chiefly mononuclear palladium species, anionic palladium nanoclusters [Pdn R(DE)n ]- , (n=2, 4, 6; DE=diene) were also observed. At short reaction times, the dinuclear complexes usually predominated, whereas at longer times the tetra- and hexanuclear clusters became relatively more abundant. In parallel, the formation of palladium black pointed to continued aggregation processes. Thus, the present study directly shows dynamic behavior of the palladium/diene catalyst system and degradation of the active catalyst with increasing reaction time.

| S-EPMC7687115 | biostudies-literature

Mechanistic studies of copper(I)-catalyzed 1,3-halogen migration.

Project description:An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.

| S-EPMC4701576 | biostudies-literature

C(alkenyl)-H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis.

Project description:A catalytic method to prepare highly substituted 1,3-dienes from two different alkenes is described using a directed, palladium(II)-mediated C(alkenyl)-H activation strategy. The transformation exhibits broad scope across three synthetically useful substrate classes masked with suitable bidentate auxiliaries (4-pentenoic acids, allylic alcohols, and bishomoallylic amines) and tolerates internal nonconjugated alkenes, which have traditionally been a challenging class of substrates in this type of chemistry. Catalytic turnover is enabled by either MnO2 as the stoichiometric oxidant or co-catalytic Co(OAc)2 and O2 (1 atm). Experimental and computational studies were performed to elucidate the preference for C(alkenyl)-H activation over other potential pathways. As part of this effort, a structurally unique alkenylpalladium(II) dimer was isolated and characterized.

| S-EPMC6089246 | 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