Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

N-Heterocyclic Carbene Ligand-Controlled Chemodivergent Suzuki-Miyaura Cross Coupling.

ABSTRACT: Two N-heterocyclic carbene ligands provide orthogonal chemoselectivity during the Pd-catalyzed Suzuki-Miyaura (SM) cross-coupling of chloroaryl triflates. The use of SIPr [SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene] leads to selective cross-coupling at chloride, while the use of SIMes [SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene] provides selective coupling at triflate. With most chloroaryl triflates and arylboronic acids, ligand-controlled selectivity is high (?10:1). The scope of this methodology is significantly more general than previously reported methods for selective SM coupling of chloroaryl triflates using phosphine ligands. Density functional theory studies suggest that palladium's ligation state during oxidative addition is different with SIMes compared to SIPr.

SUBMITTER: Reeves EK

PROVIDER: S-EPMC6754280 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

N-Heterocyclic Carbene Ligand-Controlled Chemodivergent Suzuki-Miyaura Cross Coupling.

Reeves Emily K EK Humke Jenna N JN Neufeldt Sharon R SR

The Journal of organic chemistry 20190911 18

Two N-heterocyclic carbene ligands provide orthogonal chemoselectivity during the Pd-catalyzed Suzuki-Miyaura (SM) cross-coupling of chloroaryl triflates. The use of SIPr [SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene] leads to selective cross-coupling at chloride, while the use of SIMes [SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene] provides selective coupling at triflate. With most chloroaryl triflates and arylboronic acids, ligand-controlled selec ...[more]

PMID: 31475828

Similar Datasets

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 ?- or the ?-isomeric coupling product.

| S-EPMC3776608 | biostudies-literature

Ligand-dependent stereoselective Suzuki-Miyaura cross-coupling reactions of β-enamido triflates.

Project description:The stereoselective Suzuki-Miyaura cross-coupling of (Z)-β-enamido triflates is demonstrated. Depending on the nature of the ligand in the palladium catalyst, either retention or inversion of the configuration during the synthesis of β,β-diaryl-substituted enamides is observed. Thus, the method provides synthetic access to both isomers of the target enamides from (Z)-β-enamido triflates.

| S-EPMC8561141 | 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

Suzuki-Miyaura reactions catalyzed by C₂-symmetric Pd-multi-dentate N-heterocyclic carbene complexes.

Project description:Suzuki-Miyaura coupling reactions are promoted by Pd complexes ligated with C₂-symmetric multi-dentate N-heterocyclic carbenes derived in situ from Pd(OAc)₂ and imidazolium salts. Good to excellent yields were obtained for aryl bromides as substrates. Turnover numbers of up to 10⁵ could be achieved with 5 × 10⁻⁴ mol% of Pd(OAc)₂/1 × 10⁻³ mol% NHC precatalyst in 24 h.

| S-EPMC6268461 | biostudies-literature

Copper(i)-catalyzed sulfonylative Suzuki-Miyaura cross-coupling.

Project description:Using a simple copper(i) catalyst has allowed a high yielding sulfonylative-Suzuki-Miyaura cross-coupling reaction to be developed. The process provides a single step route to diaryl sulfones from the direct combination of aryl boronic acids, sulfur dioxide and aryl iodides, and represents the first sulfonylative variant of a classic cross-coupling reaction. Sulfur dioxide is delivered from the surrogate reagent, DABSO. Variation of the reaction conditions allowed interruption of the sulfonylative-Suzuki coupling, resulting in the formation of a presumed Cu-sulfinate intermediate. These sulfinates could be trapped as their sodium salts and treated with electrophiles to allow access to arylalkyl sulfones, β-hydroxyl sulfones, sulfonamides and sulfonyl fluorides.

| S-EPMC5424447 | biostudies-literature

Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides.

Project description:Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.

| S-EPMC7456303 | biostudies-literature

Beta-aminoethyltrifluoroborates: efficient aminoethylations via Suzuki-Miyaura cross-coupling.

Project description:A set of phenethylamines has been successfully prepared via Suzuki-Miyaura cross-coupling of diverse potassium beta-aminoethyltrifluoroborates with aryl halides. The potassium beta-aminoethyltrifluoroborates were easily prepared via hydroboration of enamine and enamide precursors. [reaction: see text].

| S-EPMC2593899 | biostudies-literature

Pd-Catalyzed Suzuki-Miyaura Cross-Coupling of Pentafluorophenyl Esters.

Project description:Although the palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl esters has received significant attention, there is a lack of methods that utilize cheap and readily accessible Pd-phosphane catalysts, and can be routinely carried out with high cross-coupling selectivity. Herein, we report the first general method for the cross-coupling of pentafluorophenyl esters (pentafluorophenyl = pfp) by selective C?O acyl cleavage. The reaction proceeds efficiently using Pd(0)/phosphane catalyst systems. The unique characteristics of pentafluorophenyl esters are reflected in the fully selective cross-coupling vs. phenolic esters. Of broad synthetic interest, this report establishes pentafluorophenyl esters as new, highly reactive, bench-stable, economical, ester-based, electrophilic acylative reagents via acyl-metal intermediates. Mechanistic studies strongly support a unified reactivity scale of acyl electrophiles by C(O)?X (X = N, O) activation. The reactivity of pfp esters can be correlated with barriers to isomerization around the C(acyl)?O bond.

| S-EPMC6321476 | biostudies-literature

Suzuki-Miyaura cross-coupling optimization enabled by automated feedback.

Project description:An automated, droplet-flow microfluidic system explores and optimizes Pd-catalyzed Suzuki-Miyaura cross-coupling reactions. A smart optimal DoE-based algorithm is implemented to increase the turnover number and yield of the catalytic system considering both discrete variables-palladacycle and ligand-and continuous variables-temperature, time, and loading-simultaneously. The use of feedback allows for experiments to be run with catalysts and under conditions more likely to produce an optimum; consequently complex reaction optimizations are completed within 96 experiments. Response surfaces predicting reaction performance near the optima are generated and validated. From the screening results, shared attributes of successful precatalysts are identified, leading to improved understanding of the influence of ligand selection upon transmetalation and oxidative addition in the reaction mechanism. Dialkylbiarylphosphine, trialkylphosphine, and bidentate ligands are assessed.

| S-EPMC5123644 | biostudies-literature

Synthesis of 3-hetarylpyrroles by Suzuki–Miyaura cross-coupling

Project description:Graphical abstract 1-[tert-Butyl(diphenyl)silyl]pyrrol-3-ylboronic acid was obtained from pyrrole in three steps. Its Suzuki–Miyaura cross-coupling with functionalized pyridinyl and pyrimidinyl bromides afforded new promising 3-hetaryl-1H-pyrroles.

| S-EPMC7241993 | 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