Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Ruthenium-Catalyzed Peri- and Ortho-Alkynylation with Bromoalkynes via Insertion and Elimination.

ABSTRACT: The alkynylation of naphthols takes place with total regiocontrol at the peri position of the hydroxyl group in the presence of [RuCl₂(p-cymene)]₂ as the catalyst. This reaction features high functional group tolerance. The related ortho-alkynylation of benzoic acids proceeds under similar conditions and also shows wide functional group tolerance. Both reactions proceed through metalation, insertion of the alkyne, and bromide elimination.

SUBMITTER: Tan E

PROVIDER: S-EPMC5679662 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Ruthenium-Catalyzed Peri- and Ortho-Alkynylation with Bromoalkynes via Insertion and Elimination.

Tan Eric E Konovalov Andrey I AI Fernández Gabriela A GA Dorel Ruth R Echavarren Antonio M AM

Organic letters 20171004 20

The alkynylation of naphthols takes place with total regiocontrol at the peri position of the hydroxyl group in the presence of [RuCl2(p-cymene)]2 as the catalyst. This reaction features high functional group tolerance. The related ortho-alkynylation of benzoic acids proceeds under similar conditions and also shows wide functional group tolerance. Both reactions proceed through metalation, insertion of the alkyne, and bromide elimination. ...[more]

PMID: 28976200

Similar Datasets

Reductive Decarboxylative Alkynylation of N-Hydroxyphthalimide Esters with Bromoalkynes.

Project description:A new method for the synthesis of terminal and internal alkynes from the nickel-catalyzed decarboxylative coupling of N-hydroxyphthalimide esters and bromoalkynes is presented. This reductive cross-electrophile coupling is the first to use a C(sp)-X electrophile, and appears to proceed via an alkynylnickel intermediate. The internal alkyne products are obtained in yields of 41-95?% without the need for a photocatalyst, light, or a strong oxidant. The reaction displays a broad scope of carboxylic acid and alkyne coupling partners, and can tolerate an array of functional groups, including carbamate NH, halogen, nitrile, olefin, ketone, and ester moieties. Mechanistic studies suggest that this process does not involve an alkynylmanganese reagent and instead proceeds through nickel-mediated bond formation.

| S-EPMC5836783 | biostudies-literature

Synthesis of P-Stereogenic Benzoazaphosphole 1-Oxides via Alkynylation of P-Stereogenic ortho-Aurated and ortho-Iodo Phosphinic Amides.

Project description:An efficient methodology for the synthesis of P-stereogenic dihydrobenzoazaphosphole 1-oxides via intramolecular 5-exo-dig alkyne hydroamination promoted by tetrabutylammonium fluoride is herein described. The required chiral o-alkynylphosphinic amide starting materials were prepared in high yields under very mild reaction conditions through alkynylation of P-stereogenic (O^C)-cyclometalated (phosphinic amide)dichlorogold(III) complexes and Sonogashira cross-coupling of ortho-iodo P-stereogenic phosphinic amide.

| S-EPMC6641963 | biostudies-literature

Rhodium-catalysed ortho-alkynylation of nitroarenes.

Project description:The ortho-alkynylation of nitro-(hetero)arenes takes place in the presence of a Rh(iii) catalyst to deliver a wide variety of alkynylated nitroarenes regioselectively. These interesting products could be further derivatized by selective reduction of the nitro group or palladium-catalysed couplings. Experimental and computational mechanistic studies demonstrate that the reaction proceeds via a turnover-limiting electrophilic C-H metalation ortho to the strongly electron-withdrawing nitro group.

| S-EPMC8597868 | biostudies-literature

Effective synthesis of bicyclodienes via palladium-catalyzed asymmetric allylic alkylation and ruthenium-catalyzed cycloisomerization.

Project description:[n.3.0]Bicycles (n = 3-6) can be synthesized using palladium-catalyzed asymmetric allylic alkylation followed by ruthenium-catalyzed cycloisomerization. New types of triarylphosphino-1,2-diaminooxazoline ligands show the same high levels of enantioselectivity observed with Trost ligand when employed in Pd-catalyzed allylic alkylation reactions. The enyne products of these allylic alkylation reactions were further elaborated using a Ru-catalyzed redox isomerization process, for which a mechanism is proposed.

| S-EPMC7772093 | biostudies-literature

Diastereoselective, Zinc-Catalyzed Alkynylation of ?-Bromo Oxocarbenium Ions.

Project description:We have developed a bromination/alkynylation sequence that enables efficient transformation of simple cyclic enol ethers to difunctionalized products. The success of this strategy relies on a highly diastereselective, zinc-catalyzed addition of terminal alkynes to ?-bromo oxocarbenium ions, formed in situ via ionization of acetal precursors. Using this method, trans-?-alkynyl-?-halo pyran and furan derivatives can be prepared with high diastereoselectivity and excellent functional group tolerance.

| S-EPMC4820761 | biostudies-literature

Enantioselective copper-catalyzed alkynylation of benzopyranyl oxocarbenium ions.

Project description:We have developed highly enantioselective, copper-catalyzed alkynylations of benzopyranyl acetals. By using a copper(I) catalyst equipped with a chiral bis(oxazoline) ligand, high yields and enantioselectivities are achieved in the alkynylation of widely available, racemic isochroman and chromene acetals to deliver ?-chiral oxygen heterocycles. This method demonstrates that chiral organometallic nucleophiles can be successfully used in enantioselective additions to oxocarbenium ions.

| S-EPMC4822504 | biostudies-literature

Dinuclear Zn-catalyzed asymmetric alkynylation of unsaturated aldehydes.

Project description:Our recent development of a proline-derived bimetallic catalyst has led to a number of efficient, catalytic, enantioselective transformations. Herein, we report a practical and general alkynylation of aromatic and alpha,beta-unsaturated aldehydes using our zinc catalyst system.

| S-EPMC2596613 | biostudies-literature

Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

Project description:Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

| S-EPMC5855968 | biostudies-literature

Copper Bis(oxazoline)-Catalyzed Enantioselective Alkynylation of Benzopyrylium Ions.

Project description:The stereocontrolled construction of biologically relevant chromanones and tetrahydroxanthones has been achieved through the addition of alkynes to benzopyrylium trilfates under the influence of copper bis(oxazoline) catalysis. Excellent levels of enantiocontrol (63-98?%?ee) are achieved in the addition of a variety of alkynes to an array of chromenones with a hydrogen in the 2-position. Promising levels of enantiocontrol (54-67?%?ee) are achieved in the alkynylation of chromenones with esters in the 2-position, generating tertiary ether stereocenters resembling those frequently found in naturally occurring metabolites.

| S-EPMC7262874 | biostudies-literature

Ruthenium-catalyzed insertion of adjacent diol carbon atoms into C-C bonds: Entry to type II polyketides.

Project description:Current catalytic processes involving carbon-carbon bond activation rely on ?-unsaturated coupling partners. Exploiting the concept of transfer hydrogenative coupling, we report a ruthenium(0)-catalyzed cycloaddition of benzocyclobutenones that functionalizes two adjacent saturated diol carbon-hydrogen bonds. These regio- and diastereoselective processes enable convergent construction of type II polyketide substructures.

| S-EPMC5649382 | 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