Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Pd(II)-catalyzed enantioselective C-H activation of cyclopropanes.

ABSTRACT: Systematic ligand development has led to the identification of novel mono-N-protected amino acid ligands for Pd(II)-catalyzed enantioselective C-H activation of cyclopropanes. A diverse range of organoboron reagents can be used as coupling partners, and the reaction proceeds under mild conditions. These results provide a new retrosynthetic disconnection for the construction of enantioenriched cis-substituted cyclopropanecarboxylic acids.

SUBMITTER: Wasa M

PROVIDER: S-EPMC3241475 | biostudies-literature | 2011 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Pd(II)-catalyzed enantioselective C-H activation of cyclopropanes.

Wasa Masayuki M Engle Keary M KM Lin David W DW Yoo Eun Jeong EJ Yu Jin-Quan JQ

Journal of the American Chemical Society 20111121 49

Systematic ligand development has led to the identification of novel mono-N-protected amino acid ligands for Pd(II)-catalyzed enantioselective C-H activation of cyclopropanes. A diverse range of organoboron reagents can be used as coupling partners, and the reaction proceeds under mild conditions. These results provide a new retrosynthetic disconnection for the construction of enantioenriched cis-substituted cyclopropanecarboxylic acids. ...[more]

PMID: 22059375

Similar Datasets

Pd(II)-catalyzed enantioselective C-H activation/C-O bond formation: synthesis of chiral benzofuranones.

Project description:Pd(II)-catalyzed enantioselective C-H activation of phenylacetic acids followed by an intramolecular C-O bond formation afforded chiral benzofuranones. This reaction provides the first example of enantioselecctive C-H functionalizations through Pd(II)/Pd(IV) redox catalysis.

| S-EPMC3578945 | biostudies-literature

Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acids.

Project description:Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of monoprotected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate.

| S-EPMC2806936 | biostudies-literature

Dirhodium-Catalyzed Enantioselective Synthesis of Difluoromethylated Cyclopropanes via Enyne Cycloisomerization.

Project description:(Difluoromethylated cyclopropane represents an important motif, which is widely found in bioactive and functional molecules. Despite significant progress in modern chemistry, the atom-economic and enantioselective synthesis of difluoromethylated cyclopropanes is still challenging. Herein, an Rh2 (II)-catalyzed asymmetric enyne cycloisomerization is described to construct chiral difluoromethylated cyclopropane derivatives with up to 99% yield and 99% ee in low catalyst loading (0.2 mol%), which can be easily transformed into highly functionalized difluoromethylated cyclopropanes with vicinal all-carbon quaternary stereocenters by ozonolysis. Mechanistic studies and the crystal structures of alkyne-dirhodium complexes reveal that the cooperative weak hydrogen bondings between the substrates and the dirhodium catalyst may play key roles in this reaction.).

| S-EPMC10870034 | biostudies-literature

Pd(II)-Catalyzed Enantioselective C(sp3)-H Arylation of Free Carboxylic Acids.

Project description:A monoprotected aminoethyl amine chiral ligand based on an ethylenediamine backbone was developed to achieve Pd-catalyzed enantioselective C(sp3)-H arylation of cyclopropanecarboxylic and 2-aminoisobutyric acids without using exogenous directing groups. This new chiral catalyst affords new disconnection for preparing diverse chiral carboxylic acids from simple starting materials that are complementary to the various ring forming approaches.

| S-EPMC6038808 | biostudies-literature

Pd-Catalyzed Enantioselective Hydroalkynylation of Cyclopropenes.

Project description:We report herein an easy, mild, and robust Pd-catalyzed enantioselective hydroalkynylation reaction of achiral cyclopropenes. Commercially available Pd(acac)2 and (R)-DM-BINAP proved to be the best combination to reach high diastereo- and enantioselectivities.

| S-EPMC7493299 | biostudies-literature

Homogeneous pd-catalyzed enantioselective decarboxylative protonation.

Project description:General homogeneous conditions for the palladium-catalyzed synthesis of carbonyl compounds with tertiary carbon stereocenters at the alpha-position are reported. The highly reactive catalyst tolerates a variety of substrate substitution and functionality, and generates enantioenriched cyclic ketones from racemic allyl beta-ketoester starting materials.

| S-EPMC2966305 | biostudies-literature

Enantioselective ?-C(sp3)-H Activation of Alkyl Amines via Pd(II)/Pd(0) Catalysis.

Project description:Pd(II)-catalyzed enantioselective ?-C(sp3)-H cross-coupling of alkyl amines via desymmetrization and kinetic resolution has been realized for the first time using chiral acetyl-protected aminomethyl oxazoline ligands (APAO). A diverse range of aryl- and vinyl-boron reagents can be used as coupling partners. The chiral ?-arylated alkylamine products are further transformed into chiral 2-substituted 1,2,3,4-tetra-hydroquinolines and spiro-pyrrolidines as important structural motifs in natural products and biologically active molecules.

| S-EPMC5927623 | biostudies-literature

PdII -Catalyzed Enantioselective C(sp3 )-H Activation/Cross-Coupling Reactions of Free Carboxylic Acids.

Project description:PdII -catalyzed enantioselective C(sp3 )-H cross-coupling of free carboxylic acids with organoborons has been realized using either mono-protected amino acid (MPAA) ligands or mono-protected aminoethyl amine (MPAAM) ligands. A diverse range of aryl- and vinyl-boron reagents can be used as coupling partners to provide chiral carboxylic acids. This reaction provides an alternative approach to the enantioselective synthesis of cyclopropanecarboxylic acids and cyclobutanecarboxylic acids containing α-chiral tertiary and quaternary stereocenters. The utility of this reaction was further demonstrated by converting the carboxylic acid into cyclopropyl amine without loss of optical activity.

| S-EPMC6641982 | biostudies-literature

Pd-catalyzed enantioselective allyl-allyl cross-coupling.

Project description:The Pd-catalyzed cross-coupling of allylic carbonates and allylB(pin) is described. The regioselectivity of this reaction is sensitive to the bite angle of the ligand, with small-bite-angle ligands favoring the branched substitution product. This mode of regioselection is consistent with a reaction that operates by a 3,3' reductive elimination reaction. In the presence of appropriate chiral ligands, this reaction is rendered enantioselective and applies to both aromatic and aliphatic allylic carbonates.

| S-EPMC2925184 | biostudies-literature

Pd(II)-Catalyzed Enantioselective γ-C(sp3)-H Functionalizations of Free Cyclopropylmethylamines.

Project description:Prized for their ability to reliably forge stereocenters with precise regiocontrol from simple and abundant starting materials, substrate-directable enantioselective reactions are widely used in modern organic synthesis. As such, enantioselective C(sp3)-H functionalization reactions directed by innate functional groups could provide new routes to introduce molecular complexity within the inert hydrocarbon moiety, but to date this approach has been met with little success. While free primary aliphatic amines are common, versatile intermediates in synthesis, they are traditionally unreactive in C(sp3)-H activation reactions. Herein we report the Pd-catalyzed enantioselective C(sp3)-H functionalization of free aliphatic amines (cyclopropylmethylamines) enabled by a chiral bidentate thioether ligand. This ligand's privileged bidentate coordination mode and thioether motif favor the generation of the requisite mono(amine)-Pd(II) intermediate, thus enabling the enantioselective C-H activation of free amines. The resulting C-Pd(II) species could engage in either Pd(II)/Pd(IV) or Pd(II)/Pd(0) catalytic cycles, enabling access to a diverse range of products through (hetero)arylation, carbonylation, and olefination reactions. Consequently, this versatile reactivity offers medicinal chemists a general strategy to rapidly prepare and functionalize biologically relevant amines.

| S-EPMC7654567 | 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