Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Suzuki-Miyaura coupling of aryl carbamates, carbonates, and sulfamates.

ABSTRACT: The first Suzuki-Miyaura cross-couplings of carbamates, carbonates, and sulfamates is described. The method provides a powerful means of using simple derivatives of phenol as precursors to polysubstituted aromatic compounds, as exemplified by a concise synthesis of the anti-inflammatory drug flurbiprofen.

SUBMITTER: Quasdorf KW

PROVIDER: S-EPMC2801021 | biostudies-literature | 2009 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Suzuki-Miyaura coupling of aryl carbamates, carbonates, and sulfamates.

Quasdorf Kyle W KW Riener Michelle M Petrova Krastina V KV Garg Neil K NK

Journal of the American Chemical Society 20091201 49

The first Suzuki-Miyaura cross-couplings of carbamates, carbonates, and sulfamates is described. The method provides a powerful means of using simple derivatives of phenol as precursors to polysubstituted aromatic compounds, as exemplified by a concise synthesis of the anti-inflammatory drug flurbiprofen. ...[more]

PMID: 19928764

Similar Datasets

Suzuki-Miyaura cross-coupling of aryl carbamates and sulfamates: experimental and computational studies.

Project description:The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl(2)(PCy(3))(2) to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.

| S-EPMC3091075 | biostudies-literature

Pd-Catalyzed Suzuki-Miyaura and Hiyama-Denmark Couplings of Aryl Sulfamates.

Project description:Using a recently discovered precatalyst, the first Pd-catalyzed Suzuki-Miyaura reactions using aryl sulfamates that occur at room temperature are reported. In complementary work, it is demonstrated that a related precatalyst can facilitate the coupling of aryl silanolates, which are less toxic and reactive nucleophiles than boronic acids with aryl chlorides. By combining our results using modern electrophiles and nucleophiles, the first Hiyama-Denmark reactions using aryl sulfamates are reported.

| S-EPMC5321212 | biostudies-literature

Nickel(II) Nanoparticles Immobilized on EDTA-Modified Fe3O4@SiO2 Nanospheres as Efficient and Recyclable Catalysts for Ligand-Free Suzuki-Miyaura Coupling of Aryl Carbamates and Sulfamates.

Project description:A highly efficient and air-, thermal-, and moisture-stable nickel-based catalyst with excellent magnetic properties supported on silica-coated magnetic Fe3O4 nanoparticles was successfully synthesized. It was well characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, thermogravimetric analysis, dynamic light scattering (DLS), X-ray photoelectron spectroscopy, vibration sample magnetometry, energy-dispersive X-ray analysis, inductively coupled plasma analysis, and nitrogen adsorption-desorption isotherm analysis. The Suzuki-Miyaura coupling reaction between aryl carbamates and/or sulfamates with arylboronic acids was selected to demonstrate the catalytic activity and efficiency of the as-prepared magnetic nanocatalyst. Using the mentioned heterogeneous nanocatalyst in such reactions generated corresponding products in good to excellent yields in which the catalyst could easily be recovered from the reaction mixture with an external magnetic field to reuse directly for the next several cycles without significant loss of its activity.

| S-EPMC7144170 | biostudies-literature

Pd-catalyzed Suzuki-Miyaura cross-coupling reactions between sulfamates and potassium Boc-protected aminomethyltrifluoroborates.

Project description:Sulfamates were studied as the electrophilic partners in the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction with potassium Boc-protected primary and secondary aminomethyltrifluoroborates. A broad range of substrates was successfully coupled to provide the desired products. Complex molecules containing a new carbon-carbon bond and an aminomethyl moiety could be prepared through this developed method.

| S-EPMC3796167 | 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

Bis(dialkylphosphino)ferrocene-Ligated Nickel(II) Precatalysts for Suzuki-Miyaura Reactions of Aryl Carbonates.

Project description:Aryl carbonates, a common protecting group in synthetic organic chemistry, are potentially valuable electrophiles in cross-coupling reactions. Here, after performing a thorough evaluation of different precatalysts, we demonstrate that (dcypf)Ni(2-ethylphenyl)(Br) (dcypf = 1,1-bis-(dicyclohexylphosphino)ferrocene) is an efficient precatalyst for Suzuki-Miyaura reactions using a variety of aryl carbonates as substrates. Mechanistic studies indicate that (dcypf)Ni(2-ethylphenyl)(Br), which contains a bidentate phosphine that binds in a trans geometry, is an effective precatalyst for these reactions for two reasons: (i) it rapidly forms the Ni(O) active species and (ii) it minimizes comproportionation reactions between the Ni(O) active species and both the unactivated Ni(II) precatalyst and on-cycle Ni(II) complexes to form catalytically inactive Ni(I) species. In contrast, the state of the art precatalyst (dppf)Ni(o-tolyl)(Cl) (dppf = 1,1-bis(diphenylphosphino)ferrocene), which contains a bidentate phosphine that binds in a cis geometry, forms Ni(I) species during activation and is essentially inactive for aryl carbonate couplings. Although the exact reasons on a molecular level why the dcypf system is more active than the dppf system are unclear, our results indicate that in general Ni catalysts supported by the dcypf ligand will give better performance for catalytic reactions involving substrates which undergo relatively slow oxidative addition, such as aryl carbonates.

| S-EPMC7304551 | biostudies-literature

Iron-catalyzed alkylations of aryl sulfamates and carbamates.

Project description:The alkylation of aryl sulfamates and carbamates using iron catalysis is reported. The method constructs sp(2)-sp(3) carbon-carbon bonds and provides synthetically useful yields across a range of substrates (>35 examples). The directing group ability of sulfamates and carbamates, accompanied by their low reactivity toward conventional cross-couplings, renders these substrates useful for the synthesis of polyfunctionalized arenes.

| S-EPMC3479317 | biostudies-literature

Suzuki-Miyaura cross-coupling reactions of primary alkyltrifluoroborates with aryl chlorides.

Project description:Parallel microscale experimentation was used to develop general conditions for the Suzuki-Miyaura cross-coupling of diversely functionalized primary alkyltrifluoroborates with a variety of aryl chlorides. These conditions were found to be amenable to coupling with aryl bromides, iodides, and triflates as well. The conditions that were previously identified through similar techniques to promote the cross-coupling of secondary alkyltrifluoroborates with aryl chlorides were not optimal for the primary alkyltrifluoroborates, thus demonstrating the value of parallel experimentation to develop novel, substrate specific results.

| S-EPMC2696385 | biostudies-literature

Suzuki-Miyaura cross-coupling of potassium dioxolanylethyltrifluoroborate and aryl/heteroaryl chlorides.

Project description:A robust and efficient protocol for the introduction of the dioxolanylethyl moiety onto various aryl and heteroaryl halides has been developed, providing cross-coupling yields up to 93%. Copper-catalyzed borylation of 2-(2-bromoethyl)-1,3-dioxolane with bis(pinacolato)diboron followed by treatment with potassium bifluoride provides the key organotrifluoroborate reagent.

| S-EPMC3663905 | biostudies-literature

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

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