Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Kinzel T

PROVIDER: S-EPMC2953245 | biostudies-literature | 2010 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

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

Kinzel Tom T Zhang Yong Y Buchwald Stephen L SL

Journal of the American Chemical Society 20101001 40

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 conditi ...[more]

PMID: 20858009

Similar Datasets

Heteroaryl-Heteroaryl, Suzuki-Miyaura, Anhydrous Cross-Coupling Reactions Enabled by Trimethyl Borate.

Project description:Reaction conditions have been developed for refractory heteroaryl-heteroaryl Suzuki-Miyaura cross-couplings. The reported method employs neopentyl heteroarylboronic esters as nucleophiles, heteroaryl bromides and chlorides as the electrophiles, and the soluble base potassium trimethylsilanolate (TMSOK) under anhydrous conditions. The addition of trimethyl borate enhances reaction rates by several mechanisms, including (1) solubilization of in situ-generated boronate complexes, (2) preventing catalyst poisoning by the heteroatomic units, and (3) buffering the inhibitory effect of excess TMSOK. The use of this method enables cross-coupling of diverse reaction partners including a broad range of π-rich and π-deficient heteroaryl boronic esters and heteroaryl bromides. Reactions proceed in good yields and short reaction times (3 h or less).

| S-EPMC8892994 | 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

Exhaustive Suzuki-Miyaura reactions of polyhalogenated heteroarenes with alkyl boronic pinacol esters.

Project description:A novel Suzuki-Miyaura protocol is described that enables the exhaustive alkylation of polychlorinated pyridines. This method facilitates a formal synthesis of normuscopyridine and the rapid assembly of a dumbbell shaped portion of a [2]rotaxane.

| S-EPMC5491353 | biostudies-literature

Suzuki-Miyaura cross-coupling reactions of potassium vinyltrifluoroborate with aryl and heteroaryl electrophiles.

Project description:We have previously reported that the palladium-catalyzed cross-coupling reaction of potassium vinyltrifluoroborate with aryl electrophiles proceeds with good yields. Herein, we describe recent progress in optimizing the reaction, as well as outlining the scope and limitations of the reaction. The cross-coupling reaction can generally be effected using 2 mol % of PdCl2 and 6 mol % of PPh3 as a catalyst system in THF/H2O with Cs2CO3 as a base. Moderate to good yields are obtained in the presence of a variety of functional groups.

| S-EPMC2504465 | biostudies-literature

Palladium-Catalyzed Suzuki-Miyaura Reactions of Aspartic Acid Derived Phenyl Esters.

Project description:Transition-metal-catalyzed transformations of amino acids and peptides could provide a powerful method for their site-selective modification. Here, we report non-decarbonylative Pd-catalyzed Suzuki-Miyaura reactions of phenyl ester derivatives of aspartic acid to form aryl-amino ketones. These products are potentially important in the synthesis of pharmaceuticals, and our methodology represents a new route to access molecules of this type.

| S-EPMC6939165 | biostudies-literature

Selective and Serial Suzuki-Miyaura Reactions of Polychlorinated Aromatics with Alkyl Pinacol Boronic Esters.

Project description:Among cross-coupling reactions, the Suzuki-Miyaura transformation stands out because of its practical advantages, including the commercial availability and low toxicity of the required reagents, mild reaction conditions, and functional group compatibility. Nevertheless, few conditions can be used to cross-couple alkyl boronic acids or esters with aryl halides, especially 2-pyridyl halides. Herein, we describe two novel Suzuki-Miyaura protocols that enable selective conversion of polychlorinated aromatics, with a focus on reactions to convert 2,6-dichloropyridines to 2-chloro-6-alkylpyridines or 2-aryl-6-alkylpyridines.

| S-EPMC5433267 | biostudies-literature

<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.

Project description: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.

| S-EPMC8756804 | biostudies-literature

Differences in the Performance of Allyl Based Palladium Precatalysts for Suzuki-Miyaura Reactions.

Project description:Palladium(II) precatalysts are used extensively to facilitate cross-coupling reactions because they are bench stable and give high activity. As a result, precatalysts such as Buchwald's palladacycles, Organ's PEPPSI species, Nolan's allyl-based complexes, and Yale's 1-tert-butylindenyl containing complexes, are all commercially available. Comparing the performance of the different classes of precatalysts is challenging because they are typically used under different conditions, in part because they are reduced to the active species via different pathways. However, within a particular class of precatalyst, it is easier to compare performance because they activate via similar pathways and are used under the same conditions. Here, we evaluate the activity of different allyl-based precatalysts, such as (η3-allyl)PdCl(L), (η3-crotyl)PdCl(L), (η3-cinnamyl)PdCl(L), and (η3-1-tert-butylindenyl)PdCl(L) in Suzuki-Miyaura reactions. Specifically, we evaluate precatalyst performance as the ancillary ligand (NHC or phosphine), reaction conditions, and substrates are varied. In some cases, we connect relative activity to both the mechanism of activation and the prevalence of the formation of inactive palladium(I) dimers. Additionally, we compare the performance of in situ generated precatalysts with commonly used palladium sources such as tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3), bis(acetonitrile)dichloropalladium(II) (Pd(CH3CN)2Cl2), and palladium acetate. Our results provide information about which precatalyst to use under different conditions.

| S-EPMC7771882 | biostudies-literature

DABO Boronates: Stable Heterocyclic Boronic Acid Complexes for Use in Suzuki-Miyaura Cross-Coupling Reactions.

Project description:Diethanolamine complexed heterocyclic boronic acids (DABO boronates) are air-stable reagents that can be used directly in Suzuki-Miyaura reactions in the presence of water or a protic co-solvent. Interestingly, heterocyclic DABO boronates can be stored for extended periods of time at room temperature with no noticeable degradation, unlike their boronic acid counterparts. Heterocyclic DABO boronates constitute an operationally simple and efficient alternative to other boronic acid derivatives as coupling partners in palladium catalyzed cross-coupling reactions under standard Suzuki-Miyaura conditions.

| S-EPMC3870905 | biostudies-literature

Recoverable Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions under Thermomorphic Mode: Stille and Suzuki-Miyaura Reactions.

Project description:The reaction of [PdCl2(CH3CN)2] and bis-4,4'-(RfCH2OCH2)-2,2'-bpy (1a-d), where Rf = n-C11F23 (a), n-C10F21 (b), n-C9F19 (c) and n-C8F17 (d), respectively, in the presence of dichloromethane (CH2Cl2) resulted in the synthesis of Pd complex, [PdCl2[4,4'-bis-(RfCH2OCH2)-2,2'-bpy] (2a-d). The Pd-catalyzed Stille arylations of vinyl tributyltin with aryl halides were selected to demonstrate the feasibility of recycling usage with 2a as the catalyst using NMP (N-methyl-2-pyrrolidone) as the solvent at 120-150 °C. Additionally, recycling and electronic effect studies of 2a-c were also carried out for Suzuki-Miyaura reaction of phenylboronic acid derivatives, 4-X-C6H4-B(OH)2, (X = H or Ph) with aryl halide, 4-Y-C6H4-Z, (Y = CN, H or OCH3; Z = I or Br) in dimethylformamide (DMF) at 135-150 °C. At the end of each cycle, the product mixtures were cooled to lower temperature (e.g., -10 °C), and then catalysts were recovered by decantation with Pd leaching less than 1%. The products were quantified by gas chromatography/mass spectrometry (GC/MS) analysis or by the isolated yield. The complex 2a-catalyzed Stille reaction of aryl iodides with vinyl tributyltin have good recycling results for a total of 8 times, with a high yield within short period of time (1-3 h). Similarly, 2a-c-catalyzed Suzuki-Miyaura reactions also have good recycling results. The electronic effect studies from substituents in both Stille and Suzuki-Miyaura coupling reactions showed that electron withdrawing groups speed up the reaction rate. To our knowledge, this is the first example of recoverable fluorous long-chained Pd-catalyzed Stille reactions under the thermomorphic mode.

| S-EPMC7961810 | 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