Browse
Submit Data
Databases
API
Help

Dataset Information

32 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rhodium-catalyzed asymmetric hydroamination and hydroindolation of keto-vinylidenecyclopropanes.

ABSTRACT: We reported a highly regio- and enantioselective hydroamination and hydroindolation of keto-vinylidenecyclopropanes via cationic Rh(i) catalysis in this context. The combination of various secondary amines and indoles with keto-vinylidenecyclopropanes afforded the corresponding hydrofunctionalization products in good to excellent yields with outstanding ee values under mild conditions. A new TMM-Rh model complex was proposed, providing an atom economical Rh-?-allyl precursor at the same time. Moreover, the resulting products could easily be transformed into more complex polyheterocycles upon further synthetic manipulation.

SUBMITTER: Yang S

PROVIDER: S-EPMC5994874 | biostudies-other | 2018 Jun

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Publications

Rhodium-catalyzed asymmetric hydroamination and hydroindolation of keto-vinylidenecyclopropanes.

Yang Song S Li Quan-Zhe QZ Xu Chen C Xu Qin Q Shi Min M

Chemical science 20180511 22

We reported a highly regio- and enantioselective hydroamination and hydroindolation of keto-vinylidenecyclopropanes <i>via</i> cationic Rh(i) catalysis in this context. The combination of various secondary amines and indoles with keto-vinylidenecyclopropanes afforded the corresponding hydrofunctionalization products in good to excellent yields with outstanding ee values under mild conditions. A new TMM-Rh model complex was proposed, providing an atom economical Rh-π-allyl precursor at the same t ...[more]

PMID: 29938038

Similar Datasets

Rhodium-Catalyzed Asymmetric Hydroamination of Allyl Amines.

Project description:A Rh-catalyzed enantioselective hydroamination of allylamines using a chiral BIPHEP-type ligand is reported. Enantioenriched 1,2-diamines are formed in good yields and with excellent enantioselectivities. A diverse array of nucleophiles and amine directing groups are demonstrated, including deprotectable motifs. Finally, the methodology was demonstrated toward the rapid synthesis of 2-methyl-moclobemide.

| S-EPMC6693864 | biostudies-literature

Rhodium-catalyzed asymmetric intramolecular hydroamination of unactivated alkenes.

Project description: Not available

| S-EPMC3394429 | biostudies-literature

Asymmetric synthesis of ?-branched amines via rhodium-catalyzed reductive amination.

Project description:Amines bearing ?-stereocenters are highly important structural motifs in many biologically active compounds. However, reported enantioselective syntheses of these molecules are indirect and often require multiple steps. Herein, we report a general asymmetric route for the one-pot synthesis of chiral ?-branched amines through the highly enantioselective isomerization of allylamines, followed by enamine exchange and subsequent chemoselective reduction. This protocol is suitable for establishing various tertiary stereocenters, including those containing dialkyl, diaryl, cyclic, trifluoromethyl, difluoromethyl, and silyl substituents, which allows for a rapid and modular synthesis of many chiral ?-branched amines. To demonstrate the synthetic utility, Terikalant and Tolterodine are synthesized using this method with high levels of enantioselectivity.

| S-EPMC5864842 | biostudies-other

Rhodium(II)-catalyzed asymmetric sulfur(VI) reduction of diazo sulfonylamidines.

Project description:Diazo sulfonylamidines readily undergo enantioselective oxygen transfer from sulfur to carbon atom in the presence of chiral rhodium(II) carboxylates resulting in chiral sulfinylamidines. This unusual asymmetric atom transfer "reduction" occurs rapidly under mild conditions, and sulfinylamidines are obtained in excellent yield.

| S-EPMC3627535 | biostudies-literature

Rhodium-catalyzed asymmetric hydroboration of ?,?-unsaturated amide derivatives: ?-borylated amides.

Project description:?,?-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed ?-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the ?-borylation of ?,?-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of ?-facial selectivity.

| S-EPMC5975375 | biostudies-literature

Rhodium-catalyzed asymmetric synthesis of silicon-stereogenic silicon-bridged arylpyridinones.

Project description:A rhodium-catalyzed regio- and enantioselective synthesis of silicon-stereogenic silicon-bridged arylpyridinones has been developed through [2 + 2 + 2] cycloaddition of silicon-containing prochiral triynes with isocyanates. High yields and enantioselectivities have been achieved by employing an axially chiral monophosphine ligand, and this process could be applied to catalytic asymmetric synthesis of silicon-stereogenic chiral polymers for the first time. The reaction mechanism of the present catalysis has also been experimentally investigated to establish a reasonable catalytic cycle, advancing the mechanistic understanding of the rhodium-catalyzed pyridinone synthesis by [2 + 2 + 2] cycloaddition reactions.

| S-EPMC5975726 | biostudies-literature

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles.

Project description:A rhodium-catalyzed regio- and enantioselective cyclization of tethered allenylbenzenes is reported. Employing a RhI/Josiphos catalytic system a diverse set of 6-membered, ?-chiral benzocycles were obtained, scaffolds found in many bioactive compounds. Moreover, a gram scale reaction as well as the application of suitable transformations are demonstrated.

| S-EPMC6977554 | biostudies-literature

Rhodium(I)-Catalyzed Intermolecular Hydroacylation of α-Keto Amides and Isatins with Non-Chelating Aldehydes.

Project description:The application of the bidentate, electron-rich bisphosphine ligand, 1,3-bis(dicyclohexyl)phosphine-propane (dcpp), in rhodium(I)-catalyzed intermolecular ketone hydroacylation is herein described. Isatins and α-keto amides are shown to undergo hydroacylation with a variety of non-chelating linear and branched aliphatic aldehydes. Also reported is the synthesis of new bidentate chiral phosphine ligands, and their application in hydroacylation is discussed.

| S-EPMC4847752 | biostudies-literature

Rational Optimization of Supramolecular Catalysts for the Rhodium-Catalyzed Asymmetric Hydrogenation Reaction.

Project description:Rational design of catalysts for asymmetric transformations is a longstanding challenge in the field of catalysis. In the current contribution we report a catalyst in which a hydrogen bond between the substrate and the catalyst plays a crucial role in determining the selectivity and the rate of the catalytic hydrogenation reaction, as is evident from a combination of experiments and DFT calculations. Detailed insight allowed in silico mutation of the catalyst such that only this hydrogen bond interaction is stronger, predicting that the new catalyst is faster. Indeed, we experimentally confirmed that optimization of the catalyst can be realized by increasing the hydrogen bond strength of this interaction by going from a urea to phosphine oxide H-bond acceptor on the ligand.

| S-EPMC6123616 | biostudies-literature

Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

Project description:Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine.

| S-EPMC5989712 | 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