Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A Study of an 8-Aminoquinoline-Directed C(sp²)-H Arylation Reaction on the Route to Chiral Cyclobutane Keto Acids from Myrtenal.

ABSTRACT: This work outlines a synthetic route that can be used to access chiral cyclobutane keto acids with two stereocenters in five steps from the inexpensive terpene myrtenal. Furthermore, the developed route includes an 8-aminoquinoline-directed C(sp²)-H arylation as one of its key steps, which allows a wide range of aryl and heteroaryl groups to be incorporated into the bicyclic myrtenal scaffold prior to the ozonolysis-based ring-opening step that furnishes the target cyclobutane keto acids. This synthetic route is expected to find many applications connected to the synthesis of natural product-like compounds and small molecule libraries.

SUBMITTER: Pourghasemi Lati M

PROVIDER: S-EPMC8279478 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A Study of an 8-Aminoquinoline-Directed C(sp2)-H Arylation Reaction on the Route to Chiral Cyclobutane Keto Acids from Myrtenal.

Pourghasemi Lati Monireh M Ståhle Jonas J Meyer Michael M Verho Oscar O

The Journal of organic chemistry 20210527 12

This work outlines a synthetic route that can be used to access chiral cyclobutane keto acids with two stereocenters in five steps from the inexpensive terpene myrtenal. Furthermore, the developed route includes an 8-aminoquinoline-directed C(sp2)-H arylation as one of its key steps, which allows a wide range of aryl and heteroaryl groups to be incorporated into the bicyclic myrtenal scaffold prior to the ozonolysis-based ring-opening step that furnishes the target cyclobutane keto ac ...[more]

PMID: 34042431

Similar Datasets

Palladium-catalyzed, aminoquinoline-directed arylation of phosphonamidate and phosphinic amide sp3 C-H bonds.

Project description:Aminoquinoline-directed, palladium-catalyzed sp3 C-H bond arylation in phosphonamidates and phosphinic amides is reported. The reaction employs Pd(OAc)2 as a catalyst at 10 mol% loading and cesium phosphate or potassium carbonate as a base in 1,2-dichlorobenzene as a solvent. The directing group can be removed under basic conditions to afford phosphonic acid esters. The chemistry described here is the first example of unactivated sp3 C-H bond arylation by using a phosphorus-containing directing group.

| S-EPMC5479433 | biostudies-literature

Aminoquinoline-directed, cobalt-catalyzed carbonylation of sulfonamide sp2 C-H bonds.

Project description:We report a method for cobalt-catalyzed, aminoquinoline-directed sp2 C-H bond carbonylation of sulfonamides. The reactions proceed in a dichloroethane solvent, and employ diisopropyl azodicarboxylate as a carbon monoxide source, Mn(OAc)2 as a cooxidant and potassium pivalate as a base. Halogen, ester, and amide functionalities are compatible with the reaction conditions. This method allows for a short and efficient synthesis of saccharin derivatives.

| S-EPMC5710005 | biostudies-literature

Protometabolic Reduction of NAD+ with α-Keto Acids.

Project description:Deciphering the origins of the chemistry that supports life has frequently centered on determining prebiotically plausible paths that produce the molecules found in biology. What has been less investigated is how the energy released from the breakdown of foodstuff is coupled to the persistence of the protocell. To gain better insight into how such coupled chemistry could have emerged prebiotically, we probed the reactivity of the ribodinucleotide NAD+ with small organic molecules that were previously identified as potential constituents of protometabolism. We find that NAD+ is readily reduced nonenzymatically by α-keto acids, such as pyruvate and oxaloacetate, during oxidative decarboxylation. In the presence of FAD and a terminal electron acceptor, the consumption of α-keto acids by NAD+ initiates a plausible prebiotic electron transport chain. The observed reactivity suggests that components of the RNA world were capable of initiating the chemistry needed to capture the energy released from catabolism to drive anabolism.

| S-EPMC8395669 | biostudies-literature

Cobalt-Catalyzed, Aminoquinoline-Directed Functionalization of Phosphinic Amide sp2 C-H Bonds.

Project description:In this paper, we introduce arylphosphinic acid aminoquinoline amides as competent substrates for cobalt-catalyzed sp2 C-H bond functionalization. Specifically, the feasibility of their coupling with alkynes, alkenes, and allyl pivalate has been demonstrated. Reactions are catalyzed by simple Co(NO3)2 hydrate in ethanol or mixed dioxane/tBuOH solvent in the presence of Mn(OAc)3·2H2O additive, sodium pivalate, or acetate base and use oxygen from the air as an oxidant. Directing group removal affords ortho-functionalized P,P-diarylphosphinic acids.

| S-EPMC4980089 | biostudies-literature

Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear PdI Catalysis.

Project description:S-aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched S-aryl phosphorothioates has remained unsolved to date. We demonstrate herein the first direct C-SP(=O)(OR')(OR'') coupling of diverse and chiral phosphorothioate salts with aryl iodides, enabled by an air- and moisture-stable PdI dimer. Our mechanistic and computational data suggest distinct dinuclear PdI catalysis to be operative, which allows for operationally simple couplings with broad scope and full retention of stereochemistry.

| S-EPMC6771726 | biostudies-literature

Steric modulation of chiral biaryl diamines via Pd-catalyzed directed C-H arylation.

Project description:Palladium-catalyzed directed arylation of 2,2'-diacetamidobiaryls with aryl iodides provides efficient access to chiral ortho-substituted biaryl diamines. Aryl iodides with para- and meta-substituents are tolerated. Deprotection of the acetyl groups under basic conditions furnishes the free diamines, which should find broad utility in asymmetric catalysis.

| S-EPMC2726659 | biostudies-literature

Copper-Mediated Aminoquinoline-Directed Radiofluorination of Aromatic C-H Bonds with K18 F.

Project description:A Cu-mediated ortho-C-H radiofluorination of aromatic carboxylic acids that are protected as 8-aminoquinoline benzamides is described. The method uses K18 F and is compatible with a wide range of functional groups. The reaction is showcased in the high specific activity automated synthesis of the RARβ2 agonist [18 F]AC261066.

| S-EPMC6476334 | biostudies-literature

Organocatalytic Asymmetric Peroxidation of γ,δ-Unsaturated β-Keto Esters-A Novel Route to Chiral Cycloperoxides.

Project description:A methodology for the asymmetric peroxidation of γ,δ-unsaturated β-keto esters is presented. Using a cinchona-derived organocatalyst, the target δ-peroxy-β-keto esters were obtained in high enantiomeric ratios of up to 95:5. Additionally, these δ-peroxy esters can be readily reduced to chiral δ-hydroxy-β-keto esters without impacting the β-keto ester functionality. Importantly, this chemistry opens up a concise route to chiral 1,2-dioxolanes, a common motif in many bioactive natural products, via a novel P2O5-mediated cyclisation of the corresponding δ-peroxy-β-hydroxy esters.

| S-EPMC10254861 | biostudies-literature

Synthesis of Elaborate Benzofuran-2-carboxamide Derivatives through a Combination of 8-Aminoquinoline Directed C-H Arylation and Transamidation Chemistry.

Project description:Herein, we present a short and highly modular synthetic route that involves 8-aminoquinoline directed C-H arylation and transamidation chemistry, and which enables access to a wide range of elaborate benzofuran-2-carboxamides. For the directed C-H arylation reactions, Pd catalysis was used to install a wide range of aryl and heteroaryl substituents at the C3 position of the benzofuran scaffold in high efficiency. Directing group cleavage and further diversification of the C3-arylated benzofuran products were then achieved in a single synthetic operation through the utilization of a one-pot, two-step transamidation procedure, which proceeded via the intermediate N-acyl-Boc-carbamates. Given the high efficiency and modularity of this synthetic strategy, it constitutes a very attractive method for generating structurally diverse collections of benzofuran derivatives for small molecule screening campaigns.

| S-EPMC7024369 | biostudies-literature

Pd-catalysed ligand-enabled carboxylate-directed highly regioselective arylation of aliphatic acids.

Project description:α-amino acids bearing aromatic side chains are important synthetic units in the synthesis of peptides and natural products. Although various β-C-H arylation methodologies for amino acid derivatives involving the assistance of directing groups have been extensively developed, syntheses that directly employ N-protected amino acids as starting materials remain rare. Herein, we report an N-acetylglycine-enabled Pd-catalysed carboxylate-directed β-C(sp3)-H arylation of aliphatic acids. In this way, various non-natural amino acids can be directly prepared from phthaloylalanine in one step in good to excellent yields. Furthermore, a series of aliphatic acids have been shown to be amenable to this transformation, affording β-arylated propionic acid derivatives in moderate to good yields. More importantly, this ligand-enabled direct β-C(sp3)-H arylation could be easily scaled-up to 10 g under reflux conditions, highlighting the potential utility of this synthetic method.

| S-EPMC5384235 | biostudies-literature