Browse
Submit Data
Databases
API
Help

Dataset Information

18 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Hydroarylation of olefins catalysed by a dimeric ytterbium(II) alkyl.

ABSTRACT: Although the nucleophilic alkylation of aromatics has recently been achieved with a variety of potent main group reagents, all of this reactivity is limited to a stoichiometric regime. We now report that the ytterbium(II) hydride, [BDI^DippYbH]₂ (BDI^Dipp = CH[C(CH₃)NDipp]₂, Dipp = 2,6-diisopropylphenyl), reacts with ethene and propene to provide the ytterbium(II) n-alkyls, [BDI^DippYbR]₂ (R = Et or Pr), both of which alkylate benzene at room temperature. Density functional theory (DFT) calculations indicate that this latter process operates through the nucleophilic (S_N2) displacement of hydride, while the resultant regeneration of [BDI^DippYbH]₂ facilitates further reaction with ethene or propene and enables the direct catalytic (anti-Markovnikov) hydroarylation of both alkenes with a benzene C-H bond.

SUBMITTER: Richardson GM

PROVIDER: S-EPMC8149703 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Iron-catalysed allylation-hydrogenation sequences as masked alkyl-alkyl cross-couplings.

Project description:An iron-catalysed allylation of organomagnesium reagents (alkyl, aryl) with simple allyl acetates proceeds under mild conditions (Fe(OAc)2 or Fe(acac)2, Et2O, r.t.) to furnish various alkene and styrene derivatives. Mechanistic studies indicate the operation of a homotopic catalyst. The sequential combination of such iron-catalysed allylation with an iron-catalysed hydrogenation results in overall C(sp3)-C(sp3)-bond formation that constitutes an attractive alternative to challenging direct cross-coupling protocols with alkyl halides.

| S-EPMC9072617 | biostudies-literature

Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins.

Project description:Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

| S-EPMC5424121 | biostudies-literature

Radical Hydroarylation of Functionalized Olefins and Mechanistic Investigation of Photocatalytic Pyridyl Radical Reactions.

Project description:We report the photoredox alkylation of halopyridines using functionalized alkene and alkyne building blocks. Selective single-electron reduction of the halogenated pyridines provides the corresponding heteroaryl radicals, which undergo anti-Markovnikov addition to the alkene substrates. The system is shown to be mild and tolerant of a variety of alkene and alkyne subtypes. A combination of computational and experimental studies support a mechanism involving proton-coupled electron transfer followed by medium-dependent alkene addition and rapid hydrogen atom transfer mediated by a polarity-reversal catalyst.

| S-EPMC6495588 | biostudies-literature

Scandium-catalysed intermolecular hydroaminoalkylation of olefins with aliphatic tertiary amines.

Project description:A homoleptic scandium trialkyl complex in combination with a borate compound served as an excellent catalyst for the C-H addition of aliphatic tertiary amines to olefins. This highly regiospecific, 100% atom efficient C-H bond alkylation reaction was applicable to a wide variety of tertiary amines and olefins, including functionalised styrenes and unactivated α-olefins. This work represents the first example of rare-earth catalysed olefin hydroaminoalkylation and also the first example of catalytic C-H addition of aliphatic tertiary amines to olefins with any catalyst.

| S-EPMC5356020 | biostudies-literature

Nickel-catalysed migratory hydroalkynylation and enantioselective hydroalkynylation of olefins with bromoalkynes.

Project description:α-Chiral alkyne is a key structural element of many bioactive compounds, chemical probes, and functional materials, and is a valuable synthon in organic synthesis. Here we report a NiH-catalysed reductive migratory hydroalkynylation of olefins with bromoalkynes that delivers the corresponding benzylic alkynylation products in high yields with excellent regioselectivities. Catalytic enantioselective hydroalkynylation of styrenes has also been realized using a simple chiral PyrOx ligand. The obtained enantioenriched benzylic alkynes are versatile synthetic intermediates and can be readily transformed into synthetically useful chiral synthons.

| S-EPMC8213830 | biostudies-literature

Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines.

Project description:The intermolecular hydroamination of unactivated alkenes with simple dialkyl amines remains an unsolved problem in organic synthesis. We report a catalytic protocol for efficient additions of cyclic and acyclic secondary alkyl amines to a wide range of alkyl olefins with complete anti-Markovnikov regioselectivity. In this process, carbon-nitrogen bond formation proceeds through a key aminium radical cation intermediate that is generated via electron transfer between an excited-state iridium photocatalyst and an amine substrate. These reactions are redox-neutral and completely atom-economical, exhibit broad functional group tolerance, and occur readily at room temperature under visible light irradiation. Certain tertiary amine products generated through this method are formally endergonic relative to their constituent olefin and amine starting materials and thus are not accessible via direct coupling with conventional ground-state catalysts.

| S-EPMC5426363 | biostudies-literature

Direct, catalytic hydroaminoalkylation of unactivated olefins with N-alkyl arylamines.

Project description: Not available

| S-EPMC2590937 | biostudies-literature

Ruthenium-catalysed <i>Z</i>-selective cross metathesis of allylic-substituted olefins.

Project description:The Z-selective cross metathesis of allylic-substituted olefins is explored with recently developed ruthenium-based metathesis catalysts. The reaction proceeds with excellent stereoselectivity for the Z-isomer (typically >95%) and yields of up to 88% for a variety of allylic substituents. This includes the first synthesis of Z-α,β-unsaturated acetals by cross metathesis and their elaboration to Z-α,β-unsaturated aldehydes. In addition, the reaction is tolerant of a variety of cross partners, varying in functionality and steric profile.

| S-EPMC4339074 | biostudies-literature

Rhodium-catalysed direct hydroarylation of alkenes and alkynes with phosphines through phosphorous-assisted C-H activation.

Project description:Biarylphosphines have been widely applied as ligands in various synthetic methods, especially in transition-metal-catalysed carbon-carbon and carbon-heteroatom bond cross-coupling reactions. Based on the outstanding properties of the parent scaffolds, a general method for in situ modification of the commercial tertiary phosphine ligands to access a series of ligands is in high demand. Here we show that a rhodium-catalysed system is introduced for the hydroarylation of alkenes and alkynes with tertiary phosphines through P(III)-chelation assisted C-H activation. A series of ligand libraries containing alkyl and alkenyl substituted groups with different steric and electronic properties are obtained in high yields. Furthermore, several experimental studies are performed to uncover the key mechanistic features of the linear-selective hydroarylation of alkenes and branch-selective hydroarylation of alkynes.

| S-EPMC6684548 | biostudies-literature

Light-driven reduction of aromatic olefins in aqueous media catalysed by aminopyridine cobalt complexes.

Project description:A catalytic system based on earth-abundant elements that efficiently hydrogenates aryl olefins using visible light as the driving-force and H2O as the sole hydrogen atom source is reported. The catalytic system involves a robust and well-defined aminopyridine cobalt complex and a heteroleptic Cu photoredox catalyst. The system shows the reduction of styrene in aqueous media with a remarkable selectivity (>20 000) versus water reduction (WR). Reactivity and mechanistic studies support the formation of a [Co-H] intermediate, which reacts with the olefin via a hydrogen atom transfer (HAT). Synthetically useful deuterium-labelled compounds can be straightforwardly obtained by replacing H2O with D2O. Moreover, the dual photocatalytic system and the photocatalytic conditions can be rationally designed to tune the selectivity for aryl olefin vs. aryl ketone reduction; not only by changing the structural and electronic properties of the cobalt catalysts, but also by modifying the reduction properties of the photoredox catalyst.

| S-EPMC9006965 | 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