Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A homogeneous, recyclable polymer support for Rh(I)-catalyzed C-C bond formation.

ABSTRACT: A robust and practical polymer-supported, homogeneous, recyclable biphephos rhodium(I) catalyst has been developed for C-C bond formation reactions. Control of polymer molecular weight allowed tuning of the polymer solubility such that the polymer-supported catalyst is soluble in nonpolar solvents and insoluble in polar solvents. Using the supported rhodium catalysts, addition of aryl and vinylboronic acids to the electrophiles such as enones, aldehydes, N-sulfonyl aldimines, and alkynes occurs smoothly to provide products in high yields. Additions of terminal alkynes to enones and industrially relevant hydroformylation reactions have also been successfully carried out. Studies show that the leaching of Rh from the polymer support is low and catalyst recycle can be achieved by simple precipitation and filtration.

SUBMITTER: Jana R

PROVIDER: S-EPMC3215106 | biostudies-literature | 2011 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A homogeneous, recyclable polymer support for Rh(I)-catalyzed C-C bond formation.

Jana Ranjan R Tunge Jon A JA

The Journal of organic chemistry 20110923 20

A robust and practical polymer-supported, homogeneous, recyclable biphephos rhodium(I) catalyst has been developed for C-C bond formation reactions. Control of polymer molecular weight allowed tuning of the polymer solubility such that the polymer-supported catalyst is soluble in nonpolar solvents and insoluble in polar solvents. Using the supported rhodium catalysts, addition of aryl and vinylboronic acids to the electrophiles such as enones, aldehydes, N-sulfonyl aldimines, and alkynes occurs ...[more]

PMID: 21895010

Similar Datasets

Organic chemistry. Rh-catalyzed C-C bond cleavage by transfer hydroformylation.

Project description:The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rhodium (Xantphos)(benzoate) catalyst activates aldehyde carbon-hydrogen (C-H) bonds with high chemoselectivity to trigger carbon-carbon (C-C) bond cleavage and generate olefins at low loadings (0.3 to 2 mole percent) and temperatures (22° to 80°C). This mild protocol can be applied to various natural products and was used to achieve a three-step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton shuttle to enable transfer hydroformylation.

| S-EPMC4445961 | biostudies-literature

Rh(iii)-catalyzed regioselective intermolecular N-methylene Csp3-H bond carbenoid insertion.

Project description:A Rh(iii)-catalyzed regioselective intermolecular carbenoid insertion into the N-methylene Csp3-H bond of acyclic aliphatic amides has been achieved, taking advantage of bidentate-chelation assistance. This methodology has been successfully applied to a broad range of linear and branched-chain N-alkylamides, thus providing a practical method for the assembly of diverse beta-amino esters. Mechanism studies and density functional theory (DFT) calculations revealed that a singlet Fischer type carbene insertion via an outer-sphere pathway was involved in this N-methylene Csp3-H bond carbenoid insertion.

| S-EPMC5874982 | biostudies-literature

Rh(III)-catalyzed directed C-H bond amidation of ferrocenes with isocyanates.

Project description:[RhCp*(OAc)(2)(H(2)O)] [Cp* = pentamethylcyclopentadienyl] catalyzed the C-H bond amidation of ferrocenes possessing directing groups with isocyanates in the presence of 2 equiv/Rh of HBF(4)·OEt(2). A variety of disubstituted ferrocenes were prepared in high yields, or excellent diastereoselectivities.

| S-EPMC3511021 | biostudies-literature

Prebiotic thiol-catalyzed thioamide bond formation.

Project description:Thioamide bonds are important intermediates in prebiotic chemistry. In cyanosulfidic prebiotic chemistry, they serve as crucial intermediates in the pathways that lead to the formation of many important biomolecules (e.g., amino acids). They can also serve as purine and pyrimidine precursors, the two classes of heterocycle employed in genetic molecules. Despite their importance, the formation of thioamide bonds from nitriles under prebiotic conditions has required large excesses of sulfide or compounds with unknown prebiotic sources. Here, we describe the thiol-catalyzed formation of thioamide bonds from nitriles. We show that the formation of the simplest of these compounds, thioformamide, forms readily in spark-discharge experiments from hydrogen cyanide, sulfide, and a methanethiol catalyst, suggesting potential accumulation on early Earth. Lastly, we demonstrate that thioformamide has a Gibbs energy of hydrolysis ( ΔGr∘ ) comparable to other energy-currencies on early Earth such as pyrophosphate and thioester bonds. Overall, our findings imply that thioamides might have been abundant on early Earth and served a variety of functions during chemical evolution.

| S-EPMC11299287 | biostudies-literature

Highly Efficient Recyclable Sol Gel Polymer Catalyzed One Pot Difunctionalization of Alkynes.

Project description:Amino-bridged gel polymer P1 was discovered to catalyze alkyne halo-functionalization in excellent yields, regioselectivity, functional group compatibility, and recyclability. We have observed that both aromatic and aliphatic alkynes can be converted to ?,?-dihalogenated ketones in the presence of polymer P1 under metal-free conditions at room temperature within a short reaction time.

| S-EPMC6222667 | biostudies-literature

Asymmetric synthesis of ?-branched amines via Rh(III)-catalyzed C-H bond functionalization.

Project description:The first asymmetric intermolecular addition of non-acidic C-H bonds to imines is reported. The use of the activating N-perfluorobutanesulfinyl imine substituent is essential for achieving sufficient reactivity and provides outstanding diastereoselectivity (>98:2 dr). Straightforward removal of the sulfinyl group with HCl yields the highly enantiomerically enriched amine hydrochlorides.

| S-EPMC4105057 | biostudies-literature

Rh(III)-Catalyzed Aryl and Alkenyl C-H Bond Addition to Diverse Nitroalkenes.

Project description:The transition metal catalyzed C-H bond addition to nitroalkenes has been developed. Very broad nitroalkene scope was observed for this Rh(III)-catalyzed method, including for aliphatic, aromatic and β,β-disubstituted derivatives. Additionally, various directing groups and both aromatic and alkenyl C-H bonds were effective in this transformation. Representative nitroalkane products were converted to dihydroisoquinolones and dihydropyridones in a single step and in high yield by iron mediated reduction and in situ cyclization. Moreover, preliminary success in enantioselective Rh(III)-catalyzed C-H bond addition to nitroalkenes was achieved as was X-ray structural characterization of a nitronate intermediate.

| S-EPMC5396967 | biostudies-literature

Peptide Bond Formation Mechanism Catalyzed by Ribosome.

Project description:In this paper we present a study of the peptide bond formation reaction catalyzed by ribosome. Different mechanistic proposals have been explored by means of Free Energy Perturbation methods within hybrid QM/MM potentials, where the chemical system has been described by the M06-2X functional and the environment by means of the AMBER force field. According to our results, the most favorable mechanism in the ribosome would proceed through an eight-membered ring transition state, involving a proton shuttle mechanism through the hydroxyl group of the sugar and a water molecule. This transition state is similar to that described for the reaction in solution (J. Am. Chem. Soc. 2013, 135, 8708-8719), but the reaction mechanisms are noticeably different. Our simulations reproduce the experimentally determined catalytic effect of ribosome that can be explained by the different behavior of the two environments. While the solvent reorganizes during the chemical process involving an entropic penalty, the ribosome is preorganized in the formation of the Michaelis complex and does not suffer important changes along the reaction, dampening the charge redistribution of the chemical system.

| S-EPMC4582011 | biostudies-literature

Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors.

Project description:A Rh(III)-catalyzed C-H bond addition/primary amine-promoted cyclization of bis-Michael acceptors is reported. The C-H bond addition step occurs with high chemoselectivity, and the subsequent intramolecular Michael addition, mediated by a primary amine catalyst, sets three contiguous stereocenters with high diastereoselectivity. A broad range of directing groups and both aromatic and alkenyl C-H bonds were shown to be effective in this transformation, affording functionalized piperidines, tetrahydropyrans, and cyclohexanes.

| S-EPMC4975630 | biostudies-literature

Rh(III)-Catalyzed Diastereoselective C-H Bond Addition/Cyclization Cascade of Enone Tethered Aldehydes.

Project description:The Rh(III)-catalyzed cascade addition of a C-H bond across alkene and carbonyl π-bonds is reported. The reaction proceeds under mild reaction conditions with low catalyst loading. A range of directing groups were shown to be effective as was the functionalization of alkenyl in addition to aromatic C(sp2)-H bonds. When the enone and aldehyde electrophile were tethered together, cyclic β-hydroxy ketones with three contiguous stereocenters were obtained with high diastereoselectivity. The intermolecular three-component cascade reaction was demonstrated for both aldehyde and imine electrophiles. Moreover, the first x-ray structure of a cationic Cp*Rh(III) enolate with interatomic distances consistent with an η3-bound enolate is reported.

| S-EPMC4762265 | 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