Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rhodium(I)-catalyzed decarbonylative spirocyclization through C-C bond cleavage of benzocyclobutenones: an efficient approach to functionalized spirocycles.

ABSTRACT: The rhodium-catalyzed formation of all-carbon spirocenters involves a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through CC activation. The metal-ligand combination [{Rh(CO)2 Cl}2 ]/P(C6 F5 )3 catalyzed this transformation most efficiently. A range of diverse spirocycles were synthesized in good to excellent yields and many sensitive functional groups were tolerated. A mechanistic study supports a hydrogen-transfer process that occurs through a β-H elimination/decarbonylation pathway.

SUBMITTER: Xu T

PROVIDER: S-EPMC3970409 | biostudies-literature | 2014 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Rhodium(I)-catalyzed decarbonylative spirocyclization through C-C bond cleavage of benzocyclobutenones: an efficient approach to functionalized spirocycles.

Xu Tao T Savage Nikolas A NA Dong Guangbin G

Angewandte Chemie (International ed. in English) 20140120 7

The rhodium-catalyzed formation of all-carbon spirocenters involves a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through CC activation. The metal-ligand combination [{Rh(CO)2 Cl}2 ]/P(C6 F5 )3 catalyzed this transformation most efficiently. A range of diverse spirocycles were synthesized in good to excellent yields and many sensitive functional groups were tolerated. A mechanistic study supports a hydrogen-transfer process that occurs through a β-H elimina ...[more]

PMID: 24446067

Similar Datasets

Fe-catalyzed Decarbonylative Alkylative Spirocyclization of N-Arylcinnamamides: Access to Alkylated 1-Azaspirocyclohexadienones.

Project description:For the convenient introduction of simple linear/branched alkyl groups into biologically important azaspirocyclohexadienones, a practical Fe-catalyzed decarbonylative cascade spiro-cyclization of N-aryl cinnamamides with aliphatic aldehydes to provide alkylated 1-azaspiro-cyclohexadienones was developed. Aliphatic aldehydes were oxidative decarbonylated into primary, secondary and tertiary alkyl radicals conveniently and allows for the subsequent cascade construction of dual C(sp3)-C(sp3) and C=O bonds via radical addition, spirocyclization and oxidation sequence.

| S-EPMC7037460 | biostudies-literature

Efficient Benzimidazolidinone Synthesis via Rhodium-Catalyzed Double-Decarbonylative C-C Activation/Cycloaddition between Isatins and Isocyanates.

Project description:The first decarbonylative cycloaddition of less-strained cyclic ketones (isatins) with isocyanates is reported. Initiated by C-C activation, this distinct [5-2+2] transformation provides a rapid entry to access various benzimidazolidinone derivatives, through which a wide range of isocyanates can be efficiently coupled with broad functional group tolerance. A modified one-pot process, combining Curtius rearrangement and C-C activation, was also achieved by using acyl azides as the starting materials. Detailed mechanistic study revealed a surprising double-decarbonylative reaction pathway. The novel reactivity discovered in this basic research is expected to shed light on developing new heterocycle formation methods through a C-C/isocyanate coupling.

| S-EPMC5045044 | biostudies-literature

Palladium-catalyzed carbon-carbon bond cleavage of primary alcohols: decarbonylative coupling of acetylenic aldehydes with haloarenes.

Project description:In the current work, a palladium-catalyzed C-C bond cleavage reaction of primary alcohols has been developed. This transformation was characterized by a broad substrate scope, superior functional group tolerance, and high efficiency for selective C-C bond cleavage and was then followed by alkynyl-aryl cross coupling. Mechanism studies indicated that the propargyl alcohols underwent β-H elimination to form aldehydes rather than having undergone β-C elimination. The corresponding aldehyde intermediates then proceeded through a decarbonylation and coupling reaction with haloarenes to yield diarylacetylenes.

| S-EPMC11895861 | biostudies-literature

Sila-spirocyclization involving unstrained C(sp3)-Si bond cleavage.

Project description:C - Si Bond cleavage is one of the key elemental steps for a wide variety of silicon-based transformations. However, the cleavage of unstrained Si-C(sp3) bonds catalyzed by transition metal are still in their infancy. They generally involve the insertion of a M - C(sp2) species into the C - Si bond and consequent intramolecular C(sp2)‒Si coupling to exclusively produce siloles. Here we report the Pd-catalyzed sila-spirocyclization, in which the Si-C(sp3) bond is activated by the insertion of a M - C(sp3) species and followed by the formation of a new C(sp3)‒Si bond, allowing the construction of diverse spirosilacycles. This reactivity mode, which is strongly supported by DFT calculations may open an avenue for the Si-C(sp3) bond cleavage and silacycle synthesis.

| S-EPMC9637223 | biostudies-literature

Rhodium-Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids.

Project description:Transformation of aromatic thioesters into arylboronic esters was achieved efficiently using a rhodium catalyst. The broad functional-group tolerance and mild conditions of the method have allowed for the two-step decarboxylative borylation of a wide range of aromatic carboxylic acids, including commercially available drugs.

| S-EPMC5324605 | biostudies-literature

Concise Synthesis of Functionalized Benzocyclobutenones.

Project description:A concise approach to access functionalized benzocyclobutenones from 3-halophenol derivatives is described. This modified synthesis employs a [2+2] cycloaddition between benzynes generated from dehydrohalogenation of aryl halides using LiTMP and acetaldehyde enolate generated from n-BuLi and THF, followed by oxidation of the benzocyclobutenol intermediates to provide benzocyclobutenones. The [2+2] reaction can be run on a 10-gram scale with an increased yield. A number of functional groups including alkenes and alkynes are tolerated. Coupling of benzynes with ketene silyl acetals to give 8-substituted benzocyclobutenones is also demonstrated.

| S-EPMC4049219 | biostudies-literature

Author Correction: Sila-spirocyclization involving unstrained C(sp3)-Si bond cleavage.

Project description: Not available

| S-EPMC10465605 | biostudies-literature

Rhodium(i)-catalyzed asymmetric [4 + 2] cycloaddition reactions of 2-alkylenecyclobutanols with cyclic enones through C-C bond cleavage: efficient access to trans-bicyclic compounds.

Project description:We report a rhodium-catalyzed asymmetric formal intermolecular [4 + 2] cycloaddition reaction of 2-alkylenecyclobutanols with α,β-unsaturated cyclic ketones leading to synthetically useful trans-bicyclic molecules. Three consecutive stereogenic centers are formed in a highly enantio- and diastereoselective manner. Stepwise C-C bond cleavage and annulation are likely involved in the reaction pathway. Here, iPr-Duphos is the viable chiral ligand that promotes excellent enantio-control.

| S-EPMC5890795 | biostudies-literature

Iron(II)-catalyzed intermolecular amino-oxygenation of olefins through the N-O bond cleavage of functionalized hydroxylamines.

Project description:An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N-O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods.

| S-EPMC4183608 | biostudies-literature

Palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides by carbon-nitrogen bond activation.

Project description:Palladium-catalyzed Suzuki-Miyaura cross-coupling or aryl halides is widely employed in the synthesis of many important molecules in synthetic chemistry, including pharmaceuticals, polymers and functional materials. Herein, we disclose the first palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides for the synthesis of biaryls through the selective activation of the N-C(O) bond of amides. This new method relies on the precise sequence engineering of the catalytic cycle, wherein decarbonylation occurs prior to the transmetallation step. The reaction is compatible with a wide range of boronic acids and amides, providing valuable biaryls in high yields (>60 examples). DFT studies support a mechanism involving oxidative addition, decarbonylation and transmetallation and provide insight into high N-C(O) bond activation selectivity. Most crucially, the reaction establishes the use of palladium catalysis in the biaryl Suzuki-Miyaura cross-coupling of the amide bond and should enable the design of a wide variety of cross-coupling methods in which palladium rivals the traditional biaryl synthesis from aryl halides and pseudohalides.

| S-EPMC6977462 | 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