Browse
Submit Data
Databases
API
Help

Dataset Information

15 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

IrIII -Catalyzed Selective ortho-Monoiodination of Benzoic Acids with Unbiased C-H Bonds.

ABSTRACT: An iridium-catalyzed selective ortho-monoiodination of benzoic acids with two equivalent C-H bonds is presented. A wide range of electron-rich and electron-poor substrates undergo the reaction under mild conditions, with >20:1 mono/di selectivity. Importantly, the C-H iodination occurs selectively ortho to the carboxylic acid moiety in substrates bearing competing coordinating directing groups. The reaction is performed at room temperature and no inert atmosphere or exclusion of moisture is required. Mechanistic investigations revealed a substrate-dependent reversible C-H activation/protodemetalation step, a substrate-dependent turnover-limiting step, and the crucial role of the AgI additive in the deactivation of the iodination product towards further reaction.

SUBMITTER: Weis E

PROVIDER: S-EPMC7496429 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

IrIII -Catalyzed Selective ortho-Monoiodination of Benzoic Acids with Unbiased C-H Bonds.

Weis Erik E Johansson Magnus J MJ Martín-Matute Belén B

Chemistry (Weinheim an der Bergstrasse, Germany) 20200727 45

An iridium-catalyzed selective ortho-monoiodination of benzoic acids with two equivalent C-H bonds is presented. A wide range of electron-rich and electron-poor substrates undergo the reaction under mild conditions, with >20:1 mono/di selectivity. Importantly, the C-H iodination occurs selectively ortho to the carboxylic acid moiety in substrates bearing competing coordinating directing groups. The reaction is performed at room temperature and no inert atmosphere or exclusion of moisture is requ ...[more]

PMID: 32449557

Similar Datasets

Ni(ii)-catalyzed mono-selective ortho-arylation of unactivated aryl C-H bonds utilizing amino acids as a directing group.

Project description:The nickel(ii)-catalyzed ortho-arylation of unactivated C-H bonds utilizing amino acids as directing groups with aryl iodides or bromides as coupling electrophiles is described. This protocol features excellent mono-selectivity, good regioselectivity, and wide functional group tolerance. Additionally, the obtained products bearing a biaryl motif and an amino acid represent bioactive molecules with wide bioactivities.

| S-EPMC9062466 | biostudies-literature

Palladium-Catalyzed Decarboxylative Ortho-Acylation of Tertiary Benzamides with Arylglyoxylic Acids.

Project description:A palladium-catalyzed ortho-acylation of tertiary benzamides using arylglyoxylic acids has been described. Unlike the palladium insertion reported to occur in the distorted N-C(O) amide bond of tertiary benzamides, the current study unveils ortho C-H palladation in acylic or cyclic N,N-dialkylbenzamides affording ortho-acylated tertiary benzamides in good to excellent yields. Our experimental study on the mechanism provides information on the tendency of the amide nitrogen toward weak coordination with palladium as opposed to oxygen. However, density functional theory calculations suggest coordination of amide oxygen to palladium, which makes the mechanism especially interesting. A Pd(II)/Pd(III) catalytic cycle and nucleophilic attack by the acyl radical rather than arylglyoxylate anion are supported by mechanistic studies.

| S-EPMC6641690 | biostudies-literature

Cobalt-Catalyzed Coupling of Benzoic Acid C-H Bonds with Alkynes, Styrenes, and 1,3-Dienes.

Project description:A method for cobalt-catalyzed, carboxylate-directed functionalization of arene C-H bonds is reported. Alkynes, styrenes, and 1,3-dienes can be coupled with benzoic acids to provide cyclic products in good yields. The reactions proceed in the presence of a cobalt(II) hexafluoroacetylacetonate catalyst, (TMS)2 NH base, Ce(SO4 )2 cooxidant, and oxygen oxidant.

| S-EPMC5788714 | biostudies-literature

Rhodium(III)-Catalyzed Intramolecular Annulations of Acrylic and Benzoic Acids to Alkynes.

Project description:Rh(III) catalysts can promote a formal (4 + 2) intramolecular oxidative annulation between acrylic or benzoic acid derivatives and alkynes. The reaction, which involves a C-H activation process, allows for a rapid assembly of appealing bicyclic pyran-2-ones and tricyclic isocoumarin derivatives in moderate to good yields. The α-pyrone moiety of the products provides for further manipulations to obtain relatively complex cyclic skeletons in a very simple manner.

| S-EPMC6492232 | biostudies-literature

Palladium-catalyzed picolinamide-directed iodination of remote ortho-C-H bonds of arenes: Synthesis of tetrahydroquinolines.

Project description:A new palladium-catalyzed picolinamide (PA)-directed ortho-iodination reaction of ?-C(sp(2))-H bonds of ?-arylpropylamine substrates is reported. This reaction proceeds selectively with a variety of ?-arylpropylamines bearing strongly electron-donating or withdrawing substituents, complementing our previously reported PA-directed electrophilic aromatic substitution approach to this transformation. As demonstrated herein, a three step sequence of Pd-catalyzed ?-C(sp(3))-H arylation, Pd-catalyzed ?-C(sp(2))-H iodination, and Cu-catalyzed C-N cyclization enables a streamlined synthesis of tetrahydroquinolines bearing diverse substitution patterns.

| S-EPMC4979757 | biostudies-other

Site-Selective Copper-Catalyzed Azidation of Benzylic C-H Bonds.

Project description:Site selectivity represents a key challenge for non-directed C-H functionalization, even when the C-H bond is intrinsically reactive. Here, we report a copper-catalyzed method for benzylic C-H azidation of diverse molecules. Experimental and density functional theory studies suggest the benzyl radical reacts with a CuII-azide species via a radical-polar crossover pathway. Comparison of this method with other C-H azidation methods highlights its unique site selectivity, and conversions of the benzyl azide products into amine, triazole, tetrazole, and pyrrole functional groups highlight the broad utility of this method for target molecule synthesis and medicinal chemistry.

| S-EPMC7405889 | biostudies-literature

Ruthenium-Catalyzed C-H Arylation of Benzoic Acids and Indole Carboxylic Acids with Aryl Halides.

Project description:Herein we report the first Ru-catalyzed C-H arylation of benzoic acids with readily available aryl (pseudo)halides. The reaction, which does not require the use of silver salt additives, allows the arylation of previously challenging hindered benzoic acids and the use of generally unreactive ortho-substituted halorarenes. Furthermore, our new protocol can efficiently be applied to indole carboxylic acids, thus allowing access to C7-, C6-, C5- and C4-arylated indole compounds, a departure from the classical enhanced reactivity of the C2 and C3 positions of indole.

| S-EPMC5412846 | biostudies-other

Branch-Selective Alkene Hydroarylation by Cooperative Destabilization: Iridium-Catalyzed ortho-Alkylation of Acetanilides.

Project description:An iridium(I) catalyst system, modified with the wide-bite-angle and electron-deficient bisphosphine d(F) ppb (1,4-bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch-selective hydroarylation reactions between diverse acetanilides and aryl- or alkyl-substituted alkenes. This provides direct and ortho-selective access to synthetically challenging anilines, and addresses long-standing issues associated with related Friedel-Crafts alkylations.

| S-EPMC4691333 | biostudies-literature

Urea-Substituted Tetramethylcyclopentadienyl Ligands for Supramolecularly Accelerated RhIII -Catalyzed ortho-C-H Olefination of Benzoic Acid Derivatives.

Project description:The design and synthesis of air-stable and conveniently crystallizable RhIII -cyclopentadienyl catalysts substituted with a urea moiety, which are able to accelerate the C-H olefination of benzoic acid derivatives, is reported. Through kinetic studies and NMR titration experiments, the catalysts' substrate recognition ability mediated by hydrogen bonding was identified to be the reason for this effect. Introduction of pyridone-phosphine ligands capable of forming additional H-bond interactions increased the catalytic performance even further. By unveiling a proportionality between reaction rate and relative complex formation enthalpy the hypothesis of a supramolecular catalyst preformation was supported. Its application to a variety of substrates proved the catalyst system's advantages, generally increasing the yields when compared to the results obtained with widely used [RhCp*Cl2 ]2 .

| S-EPMC7898290 | biostudies-literature

Highly Selective Hydrogenation of C═C Bonds Catalyzed by a Rhodium Hydride.

Project description:Under mild conditions (room temperature, 80 psi of H2) Cp*Rh(2-(2-pyridyl)phenyl)H catalyzes the selective hydrogenation of the C═C bond in α,β-unsaturated carbonyl compounds, including natural product precursors with bulky substituents in the β position and substrates possessing an array of additional functional groups. It also catalyzes the hydrogenation of many isolated double bonds. Mechanistic studies reveal that no radical intermediates are involved, and the catalyst appears to be homogeneous, thereby affording important complementarity to existing protocols for similar hydrogenation processes.

| S-EPMC9366878 | biostudies-literature