Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Ruthenium(ii)-catalyzed chemoselective deacylative annulation of 1,3-diones with sulfoxonium ylides via C–C bond activation† †Electronic supplementary information (ESI) available. CCDC 1918495. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc03245b.

ABSTRACT: The first successful example of deacylative annulation of 1,3-diones with sulfoxonium ylides was achieved through Ru(ii)-catalyzed C–C bond activation. The excellent chemoselectivity and broad substrate scope render this method a practical and versatile approach for the preparation of (hetero)aryl and alkenyl substituted furans, which are valuable units in many biologically active compounds and functional materials. A preliminary mechanistic study reveals that this process involves a deacylative ?-ruthenation to generate key alkyl Ru(ii) intermediates with the release of a benzoic acid fragment.

SUBMITTER: Wen S

PROVIDER: S-EPMC6889838 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Rhodium(iii)-catalyzed annulation of enamides with sulfoxonium ylides toward isoquinolines.

Project description:An efficient rhodium(iii)-catalyzed C-H activation followed by intermolecular annulation between enamides and sulfoxonium ylides has been developed. The transformation proceeds smoothly with a broad range of substrates, affording a series of isoquinoline derivatives in moderate to good yields under additive-free conditions.

| S-EPMC8698508 | biostudies-literature

Rhodium(III)-Catalyzed [4+2] Annulation via C-H Activation: Synthesis of Multi-Substituted Naphthalenone Sulfoxonium Ylides.

Project description:A convenient Rh(III)-catalyzed C-H activation and cascade [4+2] annulation for the synthesis of naphthalenone sulfoxonium ylides has been developed. This method features perfect regioselectivity, mild and redox-neutral reaction conditions, and broad substrate tolerance with good to excellent yields. Preliminary mechanistic experiments were conducted and a plausible reaction mechanism was proposed. The new type naphthalenone sulfoxonium ylides could be further transformed into multi-substituted naphthols, which demonstrates the practical utility of this methodology.

| S-EPMC6572249 | biostudies-literature

Rhodium(iii)-catalyzed C-H annulation of 2-acetyl-1-arylhydrazines with sulfoxonium ylides: synthesis of 2-arylindoles.

Project description:An efficient Rh(iii)-catalyzed synthesis of 2-arylindole derivatives via intermolecular C-H annulation of arylhydrazines with sulfoxonium ylides was accomplished. A variety of 2-acetyl-1-arylhydrazines with sulfoxonium ylides were converted into 2-arylindoles in satisfactory yields. Excellent selectivity and good functional group tolerance of this transformation were also observed.

| S-EPMC9057399 | biostudies-literature

Ruthenium(II)-Catalyzed Homocoupling of α-Carbonyl Sulfoxonium Ylides Under Mild Conditions: Methodology Development and Mechanistic DFT Study.

Project description:A mild ruthenium(II)-catalyzed homocoupling of α-carbonyl sulfoxonium ylides was developed and the detailed mechanism was understood based on DFT calculations in the current report. The catalytic system utilizes the α-carbonyl sulfoxonium ylide as both the directing group for ortho-sp2 C-H activation and the acylmethylating reagent for C-C coupling. Various substituents are compatible in the transformation and a variety of isocoumarin derivatives were synthesized at room temperature without any protection. The theoretical results disclosed that the full catalytic cycle contains eight elementary steps, and in all the cationic Ru(II) monomer is involved as the catalytic active species. The acid additive is responsible for protonation of the ylide carbon prior to the intramolecular nucleophilic addition and C-C bond cleavage. Interestingly, the intermediacy of free acylmethylation intermediate or its enol isomer is not necessary for the transformation.

| S-EPMC7525066 | biostudies-literature

Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides.

Project description:Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96% yield and 98% enantioselectivity. Moreover, density functional theory calculations suggest that the re face of the olefin preferably attacks an iridium carbene intermediate in an asynchronous concerted step that is independent of the geometry of the olefin.

| S-EPMC9706811 | biostudies-literature

Ruthenium-catalyzed C-H bond activation and annulation of phenothiazine-3-carbaldehydes: facile access to dual-emission materials.

Project description:Reported herein is the first example of a ruthenium-catalyzed C-H activation/annulation of phenothiazine-3-carbaldehydes to construct structurally diverse pyrido[3,4-c]phenothiazin-3-iums with dual-emission characteristics. Novel organic single-molecule white-light materials based on pyrido[3,4-c]phenothiazin-3-iums with dual-emission and thermally activated delayed fluorescence (TADF) characteristics have been developed for the first time herein. Furthermore, the dual-emission molecule could be fabricated as water-dispersed NPs, which could be applied in two-channel emission intensity ratio imaging to observe the intercellular structure and can specifically target the cell membrane.

| S-EPMC11740230 | biostudies-literature

Dearomatization of benzopyrylium triflates with sulfoxonium ylides.

Project description:Benzopyrylium triflates react with sulfoxonium ylides to give rise to cyclopropanated products in up to 90% yield as a single diastereomer. The cyclopropanated products can easily undergo acid-mediated ring-expansion to afford benzo[b]oxepines. Control over the absolute stereochemistry of the process is possible when the reaction is executed under the influence of a suitable anion-binding catalyst.

| S-EPMC9885494 | biostudies-literature

Ru(ii)-catalyzed C6-selective C-H acylmethylation of pyridones using sulfoxonium ylides as carbene precursors.

Project description:In this study, we describe a method using sulfoxonium ylides as carbene precursors to achieve C6-selective acylmethylation of pyridones catalyzed by a ruthenium(ii) complex. This approach featured mild reaction conditions, moderate to excellent yields, high step economy, and had excellent functional group tolerance with good site selectivity. Besides, gram-scale preparation, synthetic utility, and mechanistic studies were conducted. It offers a direct and efficient way to synthesize pyridone derivatives.

| S-EPMC9049633 | biostudies-literature

Copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of 1,3-enynes and azomethine ylides.

Project description:Herein, we report a copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides and 1,3-enynes, which provides a series of chiral poly-substituted pyrrolidines in high regio-, diastereo-, and enantioselectivities. Both 4-aryl-1,3-enynes and 4-silyl-1,3-enynes serve as suitable dipolarophiles while 4-alkyl-1,3-enynes are inert. Moreover, the method is successfully applied in the construction of both tetrasubstituted stereogenic carbon centers and chiral spiro pyrrolidines. The DFT calculations are also conducted, which imply a concerted mechanism rather than a stepwise mechanism. Finally, various transformations started from the pyrrolidine bearing a triethylsilylethynyl group and centered on the alkyne group are achieved, which compensates for the inertness of 4-alkyl-1,3-enynes in the present reaction.

| S-EPMC10403559 | biostudies-literature

Insights into the Activation Mode of α-Carbonyl Sulfoxonium Ylides in Rhodium-Catalyzed C-H Activation: A Theoretical Study.

Project description:A computational study has been performed to investigate the mechanism of RhIII -catalyzed C-H bond activation using sulfoxonium ylides as a carbene precursor. The stepwise and concerted activation modes for sulfoxonium ylides were investigated. Detailed theoretical results showed that the favored stepwise pathway involves C-H bond activation, carbonization, carbene insertion, and protonation. The free energy profiles for dialkylation of 2-phenylpyridine were also calculated to account for the low yield of this reaction. Furthermore, the substituent effect was elucidated by comparing the energy barriers for the protonation of meta- and para-substituted sulfoxonium ylides calculated by density functional theory.

| S-EPMC9278107 | 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