Browse
Submit Data
Databases
API
Help

Dataset Information

28 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Palladium-catalyzed hydroarylation of 1,3-dienes with boronic esters via reductive formation of pi-allyl palladium intermediates under oxidative conditions.

ABSTRACT: A palladium-catalyzed reductive cross-coupling of 1,3-dienes with boronic esters in which a pi-allyl Pd species is generated directly from a 1,3-diene via a Pd-catalyzed aerobic alcohol oxidation is reported. Both the scope of the process and the origin of a highly selective 1,2-addition are discussed.

SUBMITTER: Liao L

PROVIDER: S-EPMC2911521 | biostudies-literature | 2010 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Palladium-catalyzed hydroarylation of 1,3-dienes with boronic esters via reductive formation of pi-allyl palladium intermediates under oxidative conditions.

Liao Longyan L Sigman Matthew S MS

Journal of the American Chemical Society 20100801 30

A palladium-catalyzed reductive cross-coupling of 1,3-dienes with boronic esters in which a pi-allyl Pd species is generated directly from a 1,3-diene via a Pd-catalyzed aerobic alcohol oxidation is reported. Both the scope of the process and the origin of a highly selective 1,2-addition are discussed. ...[more]

PMID: 20608751

Similar Datasets

Asymmetric palladium-catalyzed hydroarylation of styrenes and dienes.

Project description:Alkenes are desirable and highly versatile starting materials for organic transformations, and well-known substrates for palladium catalysis. Typically, these reactions result in the formation of a new alkene product via ?-hydride elimination. In contrast to this scenario, our laboratory has been involved in the development of alkene hydro- and difunctionalization reactions, where ?-hydride elimination can be controlled. We report herein the development of an asymmetric palladium-catalyzed hydroarylation, which yields diarylmethine products in up to 75% ee. Interestingly, a linear free energy relationship is observed between the steric bulk of the ligand within a certain range and the enantiomeric excess of the reaction.

| S-EPMC3129978 | biostudies-literature

Cobalt-Catalyzed Reductive Dimethylcyclopropanation of 1,3-Dienes.

Project description:Dimethylcyclopropanes are valuable synthetic targets that are challenging to access in high yield using Zn carbenoid reagents. Herein, we describe a cobalt-catalyzed variant of the Simmons-Smith reaction that enables the efficient dimethylcyclopropanation of 1,3-dienes using a Me2 CCl2 /Zn reagent mixture. The reactions proceed with high regioselectivity based on the substitution pattern of the 1,3-diene. The products are vinylcyclopropanes, which serve as substrates for transition-metal-catalyzed ring-opening reactions, including 1,3-rearrangement and [5+2] cycloaddition. Preliminary studies indicate that moderately activated monoalkenes are also amenable to dimethylcyclopropanation under the conditions of cobalt catalysis.

| S-EPMC6489504 | biostudies-literature

Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines.

Project description:Herein, we report a visible-light-mediated palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines, affording unsaturated γ- and ε-amino acid derivatives with diverse structures. In this methodology, the diazo compound readily transforms into a hybrid α-ester alkylpalladium radical with the release of dinitrogen. The radical intermediate selectively adds to the double bond of a 1,3-diene or allene, followed by the allylpalladium radical-polar crossover path and selective allylic substitution with the amine substrate, thereby leading to a single unsaturated γ- or ε-amino acid derivative. This approach proceeds under mild and simple reaction conditions and shows high functional group tolerance, especially in the incorporation of various bioactive molecules. The studies on scale-up reactions and diverse derivatizations highlight the practical utility of this multicomponent reaction protocol.

| S-EPMC10999982 | biostudies-literature

Rh(III)-catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes <i>via</i> Rh(III)-π-allyl Amidation with 1,4,2-Dioxazolones.

Project description:We herein report a modular strategy, which enables Rh(III)-catalyzed diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- and N-nucleophiles in combination with readily available 3-substituted 1,4,2-dioxazolones (78 examples, 37-91% yield). Previous attempts to functionalize the internal double bond rested on the use of plain alcoholic solvents as nucleophilic coupling partners thus dramatically limiting the scope of this transformation. We have now identified hexafluoroisopropanol as a non-nucleophilic solvent which allows the use of diverse nucleophiles and greatly expands the scope, including an unprecedented amino hydroxylation to selectively install valuable, unprotected β-amino alcohols across 1,3-dienes. Moreover, various elaborate alcohols prove to be compatible providing unique access to complex organic molecules. Finally, this method is employed in a series of intramolecular reactions to deliver valuable nitrogen heterocycles as well as γ- and δ-lactones.

| S-EPMC10569259 | biostudies-literature

Synthesis of amidines using N-allyl ynamides. A palladium-catalyzed allyl transfer through an ynamido-pi-allyl complex.

Project description:A de novo transformation of N-allyl-N-sulfonyl ynamides to amidines is described featuring a palladium-catalyzed N-to-C allyl transfer via ynamido-palladium-pi-allyl complexes.

| S-EPMC2683379 | biostudies-literature

Palladium Catalyzed Asymmetric Three-Component Coupling of Boronic Esters, Indoles, and Allylic Acetates.

Project description:Boronic esters react with 2-lithiated indoles to form boronate intermediates. The boronate reacts with allylic acetates in the presence of (BINAP)Pd catalysts to allylate C3 concurrent with alkyl migration from B to C2 of the indole. Overall, the process is a three-component coupling that joins an allylic acetate, and indole and an organo-B(pin) species to provide substituted indoles and indolines with high enantio-, regio-, and diastereoselectivity.

| S-EPMC5572568 | biostudies-literature

Palladium-catalyzed decarboxylative rearrangements of allyl 2,2,2-trifluoroethyl malonates: direct access to homoallylic esters.

Project description:Homoallylic esters are obtained in a single transformation from allyl 2,2,2-trifluoroethyl malonates by using a Pd(0) catalyst. Facile decarboxylation of allyl 2,2,2-trifluoroethyl malonates is attributed to a decrease in pK(a) compared to allyl methyl malonates. Subsequent reduction of the homoallylic 2,2,2-trifluoroethyl ester provides a (hydroxyethyl)cyclopentenyl derivative that represents a key intermediate in the synthesis of carbocyclic nucleosides. A select allyl 2,2,2-trifluoroethyl malonate undergoes a decarboxylative Claisen rearrangement to provide a regioisomeric homoallylic ester.

| S-EPMC2767373 | biostudies-literature

Palladium-Catalyzed 1,3-Difunctionalization Using Terminal Alkenes with Alkenyl Nonaflates and Aryl Boronic Acids.

Project description:A Pd-catalyzed 1,3-difunctionalization of terminal alkenes using 1,1-disubstituted alkenyl nonaflates and arylboronic acid coupling partners is reported. This transformation affords allylic arene products that are difficult to selectively access using traditional Heck cross-coupling methodologies. The evaluation of seldom employed 1,1-disubstituted alkenyl nonaflate coupling partners led to the elucidation of subtle mechanistic features of π-allyl stabilized Pd-intermediates. Good stereo- and regioselectivity for the formation of 1,3-addition products can be accessed through a minimization of steric interactions that emanate from alkenyl nonaflate substitution.

| S-EPMC5053098 | biostudies-literature

Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters.

Project description:The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.

| S-EPMC8251817 | biostudies-literature

A palladium-catalyzed three-component cross-coupling of conjugated dienes or terminal alkenes with vinyl triflates and boronic acids.

Project description:A three-component coupling of vinyl triflates and boronic acids to alkenes catalyzed by palladium is reported. Using 1,3-dienes, selective 1,2-alkene difunction-alization is observed, whereas the use of terminal alkenes results in 1,1-alkene difunctionalization. The reaction outcome is attributed to the formation of stabilized, cationic Pd-π-allyl intermediates to regulate β-hydride elimination.

| S-EPMC3084658 | 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