Browse
Submit Data
Databases
API
Help

Dataset Information

55 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

trans-Dichlorobis(XPhos)palladium(II) Precatalyst for Suzuki-Miyaura Cross-Coupling Reactions of Aryl/Vinyl Sulfonates/Halides: Scope, Mechanistic Study, and Synthetic Applications.

ABSTRACT: Suzuki-Miyaura cross-coupling reactions of aryl/vinyl sulfonates/halides with various boron species were performed using an easily available trans-dichlorobis(XPhos)palladium(II) precatalyst. Under microwave assistance, more than 30 coupling products were obtained with yields ranging from 23 to 99%, including the synthesis of two bioactive compounds, dubamine and tamoxifen. A mechanistic investigation of the Suzuki-Miyaura reaction was conducted notably by nuclear magnetic resonance (NMR) and high-resolution mass spectroscopy, revealing the nature of the active Pd⁰ species and of the reducing entity.

SUBMITTER: Sirindil F

PROVIDER: S-EPMC8756804 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

<i>trans</i>-Dichlorobis(XPhos)palladium(II) Precatalyst for Suzuki-Miyaura Cross-Coupling Reactions of Aryl/Vinyl Sulfonates/Halides: Scope, Mechanistic Study, and Synthetic Applications.

Sirindil Fatih F Pertschi Romain R Naulin Emma E Hatey Delphine D Weibel Jean-Marc JM Pale Patrick P Blanc Aurélien A

ACS omega 20211223 1

Suzuki-Miyaura cross-coupling reactions of aryl/vinyl sulfonates/halides with various boron species were performed using an easily available <i>trans</i>-dichlorobis(XPhos)palladium(II) precatalyst. Under microwave assistance, more than 30 coupling products were obtained with yields ranging from 23 to 99%, including the synthesis of two bioactive compounds, dubamine and tamoxifen. A mechanistic investigation of the Suzuki-Miyaura reaction was conducted notably by nuclear magnetic resonance (NMR) ...[more]

PMID: 35036781

Similar Datasets

Suzuki-Miyaura Coupling Enabled by Aryl to Vinyl 1,4-Palladium Migration.

Project description:The Suzuki-Miyaura coupling is a fundamentally important transformation in modern organic synthesis. The development of new reaction modes for new chemical accessibility and higher synthetic efficiency is still the consistent pursuance in this field. An efficient Suzuki-Miyaura coupling enabled by a controllable 1,4-palladium migration was realized to afford stereodefined multisubstituted olefins and 1,3-dienes. The reaction exhibits remarkable broad substrate scope, excellent functional-group tolerance, versatile conversion with obtained products, and easy scalability. The practicality of this method is highlighted by the aggregation-induced emission feature of the produced olefins and 1,3-dienes, as well as the capability of affording geometric isomer pairs with a marked difference on photoluminescent quantum yield values.

| S-EPMC7082552 | biostudies-literature

Ligand-controlled palladium-catalyzed regiodivergent Suzuki-Miyaura cross-coupling of allylboronates and aryl halides.

Project description:An orthogonal set of catalyst systems has been developed for the Suzuki-Miyaura coupling of 3,3-disubstituted and 3-monosubstituted allylboronates with (hetero)aryl halides. These methods allow for the highly selective preparation of either the α- or the γ-isomeric coupling product.

| S-EPMC3776608 | biostudies-literature

Rapidly Activating Pd-Precatalyst for Suzuki-Miyaura and Buchwald-Hartwig Couplings of Aryl Esters.

Project description:Esters are valuable electrophiles for cross-coupling due to their ubiquity and ease of synthesis. However, harsh conditions are traditionally required for the effective cross-coupling of ester substrates. Utilizing a recently discovered precatalyst, Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig reactions involving cleavage of the C(acyl)-O bond of aryl esters that proceed under mild conditions are reported. The Pd(II) precatalyst is highly active because it is reduced to the Pd(0) active species more rapidly than previous precatalysts.

| S-EPMC5786428 | biostudies-literature

A modified procedure for the palladium catalyzed borylation/Suzuki-Miyaura cross-coupling of aryl and heteroaryl halides utilizing bis-boronic acid.

Project description:A modified Pd-catalyzed method of forming aryl- and heteroarylboron species and a two-step, one-pot borylation/Suzuki-Miyaura cross coupling using the atom economical tetrahydroxydiboron (bis-boronic acid, BBA) is reported. By using ethylene glycol as an additive, the new method results in increased yields, lower BBA loading, faster reaction times, and a broader reaction scope, including previously problematic substrates such as heterocycles.

| S-EPMC4525720 | biostudies-literature

Suzuki-Miyaura cross-coupling of potassium trifluoro(N-methylheteroaryl)borates with aryl and heteroaryl halides.

Project description:The synthesis of potassium trifluoro(N-methylheteroaryl)borates and their use in cross-coupling reactions with various aryl and heteroaryl halides to construct N-methyl heteroaryl-substituted aromatic and heteroaromatic compounds are reported.

| S-EPMC3752378 | biostudies-literature

The palladium-catalyzed trifluoromethylation of vinyl sulfonates.

Project description:A method for the palladium-catalyzed trifluoromethylation of cyclohexenyl sulfonates has been developed. Various cyclohexenyl triflates and nonaflates underwent trifluoromethylation under mild reaction conditions using a catalyst system composed of Pd(dba)(2) or [(allyl)PdCl](2) and the monodentate biaryl phosphine ligand (t)BuXPhos. The trifluoromethyl anion (CF(3)(-)) or its equivalent for the process was generated in situ from TMSCF(3) in combination with KF or TESCF(3) in combination with RbF.

| S-EPMC3242697 | biostudies-literature

Palladium-catalyzed hydroxylation of aryl and heteroaryl halides enabled by the use of a palladacycle precatalyst.

Project description:A method for the hydroxylation of aryl and heteroaryl halides, promoted by a catalyst based on a biarylphosphine ligand tBuBrettPhos (L5) and its corresponding palladium precatalyst (1), is described. The reactions allow the cross-coupling of both potassium and cesium hydroxides with (hetero)aryl halides to afford a variety of phenols and hydroxylated heteroarenes in high to excellent yield.

| S-EPMC4049244 | biostudies-literature

A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki-Miyaura cross-coupling reactions of aryl halides.

Project description:A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP-Pd(II), was found to be highly active for Suzuki-Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP-Pd(II) as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups are tolerated.

| S-EPMC4273307 | biostudies-literature

DFT Investigation of Suzuki-Miyaura Reactions with Aryl Sulfamates Using a Dialkylbiarylphosphine-Ligated Palladium Catalyst.

Project description:Aryl sulfamates are valuable electrophiles for cross-coupling reactions because they can easily be synthesized from phenols and can act as directing groups for C-H bond functionalization prior to cross-coupling. Recently, it was demonstrated that (1-tBu-Indenyl)Pd(XPhos)Cl (XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) is a highly active precatalyst for room-temperature Suzuki-Miyaura couplings of a variety of aryl sulfamates. Herein, we report an in-depth computational investigation into the mechanism of Suzuki-Miyaura reactions with aryl sulfamates using an XPhos-ligated palladium catalyst. Particular emphasis is placed on the turnover-limiting oxidative addition of the aryl sulfamate C-O bond, which has not been studied in detail previously. We show that bidentate coordination of the XPhos ligand via an additional interaction between the biaryl ring and palladium plays a key role in lowering the barrier to oxidative addition. This result is supported by NBO and NCI-Plot analysis on the transition states for oxidative addition. After oxidative addition, the catalytic cycle is completed by transmetalation and reductive elimination, which are both calculated to be facile processes. Our computational findings explain a number of experimental results, including why elevated temperatures are required for the coupling of phenyl sulfamates without electron-withdrawing groups and why aryl carbamate electrophiles are not reactive with this catalyst.

| S-EPMC5967261 | biostudies-literature

A new palladium precatalyst allows for the fast Suzuki-Miyaura coupling reactions of unstable polyfluorophenyl and 2-heteroaryl boronic acids.

Project description:Boronic acids which quickly deboronate under basic conditions, such as polyfluorophenylboronic acid and five-membered 2-heteroaromatic boronic acids, are especially challenging coupling partners for Suzuki-Miyaura reactions. Nevertheless, being able to use these substrates is highly desirable for a number of applications. Having found that monodentate biarylphosphine ligands can promote these coupling processes, we developed a precatalyst that forms the catalytically active species under conditions where boronic acid decomposition is slow. With this precatalyst, Suzuki-Miyaura reactions of a wide range of (hetero)aryl chlorides, bromides, and triflates with polyfluorophenyl, 2-furan, 2-thiophene, and 2-pyrroleboronic acids and their analogues proceed at room temperature or 40 °C in short reaction times to give the desired products in excellent yields.

| S-EPMC2953245 | 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