Browse
Submit Data
Databases
API
Help

Dataset Information

30 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

ABSTRACT: A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM-IMDAR protocols.

SUBMITTER: Miro J

PROVIDER: S-EPMC4578421 | biostudies-literature | 2015

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

Miró Javier J Sánchez-Roselló María M Sanz Álvaro Á Rabasa Fernando F Del Pozo Carlos C Fustero Santos S

Beilstein journal of organic chemistry 20150825

A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in ...[more]

PMID: 26425205

Similar Datasets

New and concise syntheses of the bicyclic oxamazin core using an intramolecular nitroso Diels-Alder reaction and ring-closing olefin metathesis.

Project description:Herein two new and concise synthetic approaches for making an unsaturated bicyclic oxamazin core are reported. The first involves the use of an intramolecular Diels-Alder reaction to form both of the fused rings in one step. The second approach incorporates ring-closing olefin metathesis in the final step to form the second fused ring of the core. The scope of the second approach was also expanded further to afford larger ringed bicyclic systems.

| S-EPMC3656481 | biostudies-literature

Synthesis of mixed musks <i>via</i> Eschenmoser-Tanabe fragmentation, enyne metathesis and Diels-Alder reaction as key steps.

Project description:Musk analogues containing different macrocyclic ring systems as well as different annulated ring systems were synthesised by a simple and useful strategy. This strategy includes Eschenmoser-Tanabe fragmentation, enyne metathesis and Diels-Alder reaction as key steps. Starting from easily available (n) macrocyclic ketones, (n + 3) macrocyclic systems were assembled using the basic organic reactions.

| S-EPMC9092383 | biostudies-literature

Type 2 intramolecular N-acylazo Diels-Alder reaction: regio- and stereoselective synthesis of bridgehead bicyclic 1,2-diazines.

Project description:The type 2 intramolecular N-acylazo Diels-Alder reaction provides a regio- and stereoselective synthesis of bicyclic 1,2-diazine systems. A new method for the generation of N-acylazo dienophiles with tetra-n-butylammonium periodate is reported. X-ray crystallographic analysis allowed the quantification of structural distortions of the nonplanar bridgehead olefin and lactam functionalities in 1,2-diazine cycloadducts 11 and 15. Caprolactams and enantholactams were formed by stereoselective bridgehead alkene reduction, a process that transfers stereochemistry from the bridgehead lactam nitrogen to the bridgehead carbon. The sequence of transformations offers a convenient route for the diastereoselective synthesis of medium-ring nitrogen heterocycles and 1,4-diamines.

| S-EPMC3192005 | biostudies-literature

Intramolecular Diels-Alder reactions of cyclopropenone ketals.

Project description:The first intramolecular cycloaddition reactions of cyclopropenone ketals with tethered electron-deficient, electron-rich, and neutral 1-substituted dienes are reported, constituting inverse electron demand, normal, and neutral Diels-Alder reactions, that provide exclusively the exo [4 + 2] cycloaddition products without the intervention of [1 + 2], [3 + 2], or [3 + 4] cycloadducts in reactions whose courses do not depend on the reaction conditions, the diene activating substituent, or the nature of the tethering.

| S-EPMC2912946 | biostudies-literature

A Diels-Alder Route to Angularly Functionalized Bicyclic Structures.

Project description:A Diels-Alder based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step.

| S-EPMC2921539 | biostudies-literature

Mechanism of the Intramolecular Hexadehydro-Diels-Alder Reaction.

Project description:Theoretical analysis of the mechanism of the intramolecular hexadehydro-Diels-Alder (HDDA) reaction, validated against prior and newly measured kinetic data for a number of different tethered yne-diynes, indicates that the reaction proceeds in a highly asynchronous fashion. The rate-determining step is bond formation at the alkyne termini nearest the tether, which involves a transition-state structure exhibiting substantial diradical character. Whether the reaction then continues to close the remaining bond in a concerted fashion or in a stepwise fashion (i.e., with an intervening intermediate) depends on the substituents at the remaining terminal alkyne positions. Computational modeling of the HDDA reaction is complicated by the significant diradical character that arises along the reaction coordinate, which leads to instabilities in both restricted singlet Kohn-Sham density functional theory (DFT) and coupled cluster theory based on a Hartree-Fock reference wave function. A consistent picture emerges, however, from comparison of broken-symmetry DFT calculations and second-order perturbation theory based on complete-active-space self-consistent-field (CASPT2) calculations.

| S-EPMC4729778 | biostudies-literature

Intramolecular Diels-Alder reactions of siloxacyclopentene constrained trienes.

Project description:The synthesis of siloxacyclopentene-constrained trienes 7 and 10 and studies of their IMDA cycloadditions are described. The use of appropriately chosen thermal or Lewis acid conditions allows for cycloadducts 3-6 to be obtained with high levels of diastereoselectivity. These adducts possess trans-relationships between the hydroxyl group and the adjacent ring fusion proton, a stereochemical relationship not previously attainable in IMDA reactions.

| S-EPMC2504012 | biostudies-literature

A rhodium catalyzed cycloisomerization and tandem Diels-Alder reaction for facile access to diverse bicyclic and tricyclic heterocycles.

Project description:A regioselective distal cycloisomerization of 1,6-allenenes was successfully developed to afford six-membered ring exocyclic 1,3-dienes employing a rhodium/diphosphine catalyst system. Deuterium labelling experiments and DFT calculations were performed to provide insights into the reaction mechanism of this unprecedented transformation. In addition, one-pot tandem Diels-Alder reactions with various dienophiles could readily construct diverse bicyclic and tricyclic nitrogen heterocycles, which are ubiquitous core scaffolds for a variety of natural products and bioactives. High efficiency and exclusive chemo and regioselectivities for a broad substrate scope were achieved under mild conditions using a low catalyst loading of 0.5 mol%.

| S-EPMC6521805 | biostudies-literature

Microwave-based reaction screening: tandem retro-Diels-Alder/Diels-Alder cycloadditions of o-quinol dimers.

Project description:We have accomplished a parallel screen of cycloaddition partners for o-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of o-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of o-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor.

| S-EPMC3214659 | biostudies-literature

5-Hydroxyindoles by intramolecular alkynol-furan diels-alder cycloaddition.

Project description:A convergent approach provides a convenient access to synthetically and biologically useful 3,4-disubstituted 5-hydroxyindoles. The one-pot procedure uses microwave heating to initiate an intramolecular [4 + 2]-cycloaddition of an alkynol segment onto a furan followed by a fragmentation, aromatization, and N-Boc deprotection cascade. Yields range from 15 to 74%, with aromatic substituents providing better conversions. 4-Trimethylsilylated analogues undergo a 1,3-silatropic rearrangement to give the O-TMS ethers.

| S-EPMC3684082 | 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