Browse
Submit Data
Databases
API
Help

Dataset Information

18 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Mechanism of the rhodium(III)-catalyzed arylation of imines via C-H bond functionalization: inhibition by substrate.

ABSTRACT: Rh(III)-catalyzed arylation of imines provides a new method for C-C bond formation while simultaneously introducing an ?-branched amine as a functional group. This detailed mechanistic study provides insights for the rational future development of this new reaction. Relevant intermediate Rh(III) complexes have been isolated and characterized, and their reactivities in stoichiometric reactions with relevant substrates have been monitored. The reaction was found to be first order in the catalyst resting state and inverse first order in the C-H activation substrate.

SUBMITTER: Tauchert ME

PROVIDER: S-EPMC3269099 | biostudies-literature | 2012 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Mechanism of the rhodium(III)-catalyzed arylation of imines via C-H bond functionalization: inhibition by substrate.

Tauchert Michael E ME Incarvito Christopher D CD Rheingold Arnold L AL Bergman Robert G RG Ellman Jonathan A JA

Journal of the American Chemical Society 20120117 3

Rh(III)-catalyzed arylation of imines provides a new method for C-C bond formation while simultaneously introducing an α-branched amine as a functional group. This detailed mechanistic study provides insights for the rational future development of this new reaction. Relevant intermediate Rh(III) complexes have been isolated and characterized, and their reactivities in stoichiometric reactions with relevant substrates have been monitored. The reaction was found to be first order in the catalyst r ...[more]

PMID: 22257031

Similar Datasets

Rhodium(III)-catalyzed arylation of Boc-imines via C-H bond functionalization.

Project description:The first rhodium-catalyzed arylation of imines proceeding via C-H bond functionalization is reported. Use of a non-coordinating halide abstractor is important to obtain reactivity. Aryl-branched N-Boc-amines are formed, and a wide range of functionality is compatible with the reaction.

| S-EPMC3045530 | biostudies-literature

Rhodium(III)-catalyzed indazole synthesis by C-H bond functionalization and cyclative capture.

Project description:An efficient, one-step, and highly functional group-compatible synthesis of substituted N-aryl-2H-indazoles is reported via the rhodium(III)-catalyzed C-H bond addition of azobenzenes to aldehydes. The regioselective coupling of unsymmetrical azobenzenes was further demonstrated and led to the development of a new removable aryl group that allows for the preparation of indazoles without N-substitution. The 2-aryl-2H-indazole products also represent a new class of readily prepared fluorophores for which initial spectroscopic characterization has been performed.

| S-EPMC3656829 | biostudies-other

Rhodium(III)-catalyzed alkenyl C-H bond functionalization: convergent synthesis of furans and pyrroles.

Project description:Ring in the new: a new annulation for the efficient synthesis of substituted furans and pyrroles is reported. The Rh(III) -catalyzed reaction of O-methyl α,β-unsaturated oximes with aldehydes and N-tosyl imines affords secondary alcohol and amine intermediates, respectively. Cyclization and aromatization occurs under the reaction conditions to provide access to biologically relevant furans and pyrroles in good yields. Cp*=C(5)Me(5), DCE=1,2-dichloroethane, THF=tetrahydrofuran.

| S-EPMC3770945 | biostudies-literature

Thioketone-directed rhodium(I) catalyzed enantioselective C-H bond arylation of ferrocenes.

Project description:Planar chiral ferrocenes have received great attention in both academia and industry. Although remarkable progresses have been made over the past decade, the development of efficient and straightforward methods for the synthesis of enantiopure planar chiral ferrocenes remains highly challenging. Herein, we report a rhodium(I)/phosphonite catalyzed thioketone-directed enantioselective C-H bond arylation of ferrocenes. Readily available aryl iodides are used as the coupling partners in this transformation, leading to a series of planar chiral ferrocenes in good yields and excellent enantioselectivities (up to 86% yield, 99% ee). Of particular note, heteroaryl coupled ferrocenes, which are difficult to access with previous approaches, can be obtained in satisfactory results.

| S-EPMC6744407 | biostudies-other

Synthesis of Azolo[1,3,5]triazines via Rhodium(III)-Catalyzed Annulation of N-Azolo Imines and Dioxazolones.

Project description:A wide range of azolo[1,3,5]triazines were obtained by Rh(III)-catalyzed annulation of N-azolo imines and dioxazolones. The reaction proceeds by the first catalytic C-H amidation of an imidoyl C-H bond followed by cyclodehydration. Good yields were obtained for N-azolo imines derived from aminoazoles and aromatic and heteroaromatic aldehydes. A range of dioxazolone amidating reagents were employed to introduce aryl, heteroaryl, and alkyl substituents. The reaction was also performed with a benchtop setup at 1 mmol scale using microwave heating.

| S-EPMC6097942 | biostudies-literature

Branch-selective reductive coupling of 2-vinyl pyridines and imines via rhodium catalyzed C-C bond forming hydrogenation.

Project description:Hydrogenation of 2-vinyl azines 1a-1e in the presence of N-arylsulfonyl imines 2a-2l at ambient temperature and pressure employing cationic rhodium catalysts ligated by tri-2-furylphosphine results in regioselective reductive coupling to furnish branched products of imine addition 3a-3v, which embody modest to high levels of syn-diastereoselectivity. Catalytic coupling of 6-bromo-2-vinylpyridine 1a to imine 2l under an atmosphere of elemental deuterium provides deuterio-3l, with deuterium exclusively at the former beta-position of the vinyl moiety. These data are consistent with a catalytic mechanism involving oxidative coupling of the vinyl azine and imine partners to furnish a cationic aza-rhodacyclopentane, which upon deuteriolytic cleavage releases the adduct and regenerates cationic rhodium(I) to close the catalytic cycle. These studies represent the first metal catalyzed reductive C-C couplings of vinyl azines.

| S-EPMC2844715 | biostudies-literature

Enantioselective Synthesis of Spiroindenes by Enol-Directed Rhodium(III)-Catalyzed C-H Functionalization and Spiroannulation.

Project description:Chiral cyclopentadienyl rhodium complexes promote highly enantioselective enol-directed C(sp(2))-H functionalization and oxidative annulation with alkynes to give spiroindenes containing all-carbon quaternary stereocenters. High selectivity between two possible directing groups, as well as control of the direction of rotation in the isomerization of an O-bound rhodium enolate into the C-bound isomer, appear to be critical for high enantiomeric excesses.

| S-EPMC4648053 | biostudies-literature

Rhodium-catalyzed, P-directed selective C7 arylation of indoles.

Project description:The indole scaffold will continue to play a vital role in the future of drug discovery and agrochemical development. Regioselective direct arylation of indoles on the benzenoid moiety is a challenging task due to the inherent reactivity of the C2 and C3 positions. Here, we have developed an effective strategy for the regioselective direct arylation of indoles at the C7 position with (hetero)aryl bromides by the rational design of a directing group. The key to the high selectivity and reactivity of this method is the appropriate selection of a class of directing groups, N-PR2 (R = t Bu and c Hex), that are easily removed in the presence of the Wilkinson's catalyst. Using the present method as a key step, formal synthesis of marine alkaloid dictyodendrin B has also been demonstrated.

| S-EPMC6294599 | 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

Enantioselective rhodium-catalyzed [4+2] cycloaddition of ?,?-unsaturated imines and isocyanates.

Project description:A [4+2] cycloaddition of ?,?-unsaturated imines and isocyanates catalyzed by a phosphoramidite-rhodium complex provides pyrimidinones in good yields and high enantioselectivities.

| S-EPMC3069138 | 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