Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

1,2-N-migration in a gold-catalysed synthesis of functionalised indenes by the 1,1-carboalkoxylation of ynamides.

ABSTRACT: Unique ?-hemiaminal ether gold carbene intermediates were accessed by a gold-catalysed 1,1-carboalkoxylation strategy and evolved through a highly selective 1,2-N-migration. This skeletal rearrangement gave functionalised indenes, and isotopic labelling confirmed the rare C-N bond cleavage of the ynamide moiety. The effect of substituents on the migration has been explored, and a model is proposed to rationalise the observed selectivity.

SUBMITTER: Adcock HV

PROVIDER: S-EPMC4204129 | biostudies-literature | 2014 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

1,2-N-migration in a gold-catalysed synthesis of functionalised indenes by the 1,1-carboalkoxylation of ynamides.

Adcock Holly V HV Langer Thomas T Davies Paul W PW

Chemistry (Weinheim an der Bergstrasse, Germany) 20140514 24

Unique α-hemiaminal ether gold carbene intermediates were accessed by a gold-catalysed 1,1-carboalkoxylation strategy and evolved through a highly selective 1,2-N-migration. This skeletal rearrangement gave functionalised indenes, and isotopic labelling confirmed the rare C-N bond cleavage of the ynamide moiety. The effect of substituents on the migration has been explored, and a model is proposed to rationalise the observed selectivity. ...[more]

PMID: 24828030

Similar Datasets

Gold Catalysed Redox Synthesis of Imidazo[1,2-a]pyridine using Pyridine N-Oxide and Alkynes.

Project description:A mild, catalytic, atom economical synthesis of imidazo[1,2-a]pyridines has been developed: catalytic PicAuCl2 in the presence of an acid produces a range imidazo[1,2-a]pyridines in good yield. This strategy is mild and forseen to be of particular use for the installation of stereogenic centers adjacent to the imidazo[1,2-a]pyridine ring without loss of enantiomeric excess.

| S-EPMC4019451 | biostudies-literature

Gold(I)-catalyzed enantioselective carboalkoxylation of alkynes.

Project description:A highly enantioselective carboalkoxylation of alkynes catalyzed by cationic (DTBM-MeO-Biphep)gold(I) complexes is reported. Various optically active ?-alkoxyindanone derivatives were obtained in good yields with high enantioselectivities. Furthermore, this methodology was extended to the enantioselective synthesis of 3-methoxycyclopentenones. The reaction is proposed to proceed through an enantioselective cyclization of intermediates containing vinylgold(I) and prochiral oxocarbenium moieties.

| S-EPMC3795527 | biostudies-literature

Mechanistic studies of an unprecedented enzyme-catalysed 1,2-phosphono-migration reaction.

Project description:(S)-2-hydroxypropylphosphonate ((S)-2-HPP) epoxidase (HppE) is a mononuclear non-haem-iron-dependent enzyme responsible for the final step in the biosynthesis of the clinically useful antibiotic fosfomycin. Enzymes of this class typically catalyse oxygenation reactions that proceed via the formation of substrate radical intermediates. By contrast, HppE catalyses an unusual dehydrogenation reaction while converting the secondary alcohol of (S)-2-HPP to the epoxide ring of fosfomycin. Here we show that HppE also catalyses a biologically unprecedented 1,2-phosphono migration with the alternative substrate (R)-1-HPP. This transformation probably involves an intermediary carbocation, based on observations with additional substrate analogues, such as (1R)-1-hydroxyl-2-aminopropylphosphonate, and model reactions for both radical- and carbocation-mediated migration. The ability of HppE to catalyse distinct reactions depending on the regio- and stereochemical properties of the substrate is given a structural basis using X-ray crystallography. These results provide compelling evidence for the formation of a substrate-derived cation intermediate in the catalytic cycle of a mononuclear non-haem-iron-dependent enzyme. The underlying chemistry of this unusual phosphono migration may represent a new paradigm for the in vivo construction of phosphonate-containing natural products that can be exploited for the preparation of new phosphonate derivatives.

| S-EPMC3725809 | biostudies-literature

Copper-Promoted Regioselective Intermolecular Diamination of Ynamides: Synthesis of Imidazo[1,2-<i>a</i>]pyridines.

Project description:A facile access to 3-heterosubstituted (3-oxazolidinonyl/indolyl/phenoxy) imidazo[1,2-a]pyridines from readily available 2-aminopyridines and electron-rich (internally activated) alkynes like ynamides/ynamines/ynol ethers is achieved via Cu(OTf)2-mediated intermolecular diamination under aerobic conditions. The reaction is highly regioselective, owing to internal electron bias, and thus led to a single regioisomer with heterosubstitution at C3.

| S-EPMC6641143 | biostudies-literature

Gold-Catalyzed Atroposelective Synthesis of 1,1'-Binaphthalene-2,3'-diols.

Project description:A highly atroposelective (up to 97?% ee) Au-catalyzed synthesis of 1,1'-binaphthalene-2,3'-diols is reported starting from a range of substituted benzyl alkynones. Essential for the achievement of high enantioselectivity during the key assembly of the naphto-3-ol unit is the use of TADDOL-derived ?-cationic phosphonites as ancillary ligands. Preliminary results demonstrate that the transformation of the obtained binaphthyls into axially chiral monodentate phosphines is possible without degradation of enantiopurity.

| S-EPMC7155015 | biostudies-literature

Gold(I)-catalysed synthesis of a furan analogue of thiamine pyrophosphate.

Project description:An analogue of thiamine having a furan ring in place of the thiazolium ring has been synthesised by a short and efficient route, involving gold(I)-catalysed cyclisation of an alkynyl alcohol to form the furan ring. The furan analogue of thiamine diphosphate (ThDP) was also made and tested for binding to and inhibition of pyruvate decarboxylase (PDC) from Zymomonas mobilis (overexpressed in E. coli with a N-terminal His-tag). It is a very strong inhibitor, with a K i value of 32.5 pM. It was also shown that the furan analogue of thiamine can be functionalised at the C-2 position, which will allow access to mimics of reaction intermediates of various ThDP-dependent enzymes.

| S-EPMC4222410 | biostudies-literature

Gold film-catalysed benzannulation by microwave-assisted, continuous flow organic synthesis (MACOS).

Project description:Methodology has been developed for laying down a thin gold-on-silver film on the inner surface of glass capillaries for the purpose of catalysing benzannulation reactions. The cycloaddition precursors are flowed through these capillaries while the metal film is being heated to high temperatures using microwave irradiation. The transformation can be optimized rapidly, tolerates a wide number of functional groups, is highly regioselective, and proceeds in good to excellent conversion.

| S-EPMC2748690 | biostudies-literature

Palladium(II)-Catalysed Aminocarbonylation of Terminal Alkynes for the Synthesis of 2-Ynamides: Addressing the Challenges of Solvents and Gas Mixtures.

Project description:2-Ynamides can be synthesised through PdII catalysed oxidative carbonylation, utilising low catalyst loadings. A variety of alkynes and amines can be used to afford 2-ynamides in high yields, whilst overcoming the drawbacks associated with previous oxidative methods, which rely on dangerous solvents and gas mixtures. The use of [NBu4 ]I allows the utilisation of the industrially recommended solvent ethyl acetate. O2 can be used as the terminal oxidant, and the catalyst can operate under safer conditions with low O2 concentrations.

| S-EPMC5347853 | biostudies-literature

N-Heterocyclic carbene catalysed redox isomerisation of esters to functionalised benzaldehydes.

Project description:N-Heterocyclic carbene catalysed redox isomerisation with reduction about the carbonyl has been developed in the transformation of trienyl esters to tetrasubstituted benzaldehydes. The reaction proceeds in good to excellent yield, and in cases that provide 2,2'-biaryls, enantioselectivity is observed. Mechanistic studies demonstrate the intermediacy of a cyclohexenyl β-lactone, while implicating formation of the homoenolate as turnover limiting.

| S-EPMC5645917 | biostudies-literature

Gold(I)-catalysed one-pot synthesis of chromans using allylic alcohols and phenols.

Project description:A gold(I)-catalysed reaction of allylic alcohols and phenols produces chromans regioselectively via a one-pot Friedel-Crafts allylation/intramolecular hydroalkoxylation sequence. The reaction is mild, practical and tolerant of a wide variety of substituents on the phenol.

| S-EPMC3778418 | 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