Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

An intramolecular inverse electron demand Diels-Alder approach to annulated ?-carbolines.

ABSTRACT: Intramolecular inverse electron demand cycloadditions of isatin-derived 1,2,4-triazines with acetylenic dienophiles tethered by amidations or transesterifications proceed in excellent yields to produce lactam- or lactone-fused ?-carbolines. Beginning with various isatins and alkynyl dienophiles, a pilot-scale library of eighty-eight ?-carbolines was prepared by using this robust methodology for biological evaluation.

SUBMITTER: Ma Z

PROVIDER: S-EPMC3388871 | biostudies-other | 2012

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Publications

An intramolecular inverse electron demand Diels-Alder approach to annulated α-carbolines.

Ma Zhiyuan Z Ni Feng F Woo Grace H C GH Lo Sie-Mun SM Roveto Philip M PM Schaus Scott E SE Snyder John K JK

Beilstein journal of organic chemistry 20120606

Intramolecular inverse electron demand cycloadditions of isatin-derived 1,2,4-triazines with acetylenic dienophiles tethered by amidations or transesterifications proceed in excellent yields to produce lactam- or lactone-fused α-carbolines. Beginning with various isatins and alkynyl dienophiles, a pilot-scale library of eighty-eight α-carbolines was prepared by using this robust methodology for biological evaluation. ...[more]

PMID: 23015831

Similar Datasets

Approach Matters: The Kinetics of Interfacial Inverse-Electron Demand Diels-Alder Reactions.

Project description:Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels-Alder (IEDDA) reactions represent a promising metal-free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained by surface-bound mass spectrometry (DART-HRMS).

| S-EPMC5637934 | biostudies-literature

Lewis acid catalyzed inverse-electron-demand Diels-Alder reaction of tropones.

Project description:Lewis acid catalyzed inverse-electron-demand Diels-Alder reaction of tropone derivatives was developed. Up to 97% ee was obtained for the chiral dinucleus BINOL-aluminum complex catalyzed reaction between tropones and ketene diethyl acetal to give bicyclo[3.2.2] ring structures, which opens up a unique way of making chiral seven-membered rings.

| S-EPMC2810398 | biostudies-literature

Hydrolytically Degradable PEG-Based Inverse Electron Demand Diels-Alder Click Hydrogels.

Project description:Hydrogels cross-linked by inverse electron demand Diels-Alder (iEDDA) click chemistry are increasingly used in biomedical applications. With a few exceptions in naturally derived and chemically modified macromers, iEDDA click hydrogels exhibit long-term hydrolytic stability, and no synthetic iEDDA click hydrogels can undergo accelerated and tunable hydrolytic degradation. We have previously reported a novel method for synthesizing norbornene (NB)-functionalized multiarm poly(ethylene glycol) (PEG), where carbic anhydride (CA) was used to replace 5-norbornene-2-carboxylic acid. The new PEGNBCA-based thiol-norbornene hydrogels exhibited unexpected fast yet highly tunable hydrolytic degradation. In this contribution, we leveraged the new PEGNBCA macromer for forming iEDDA click hydrogels with [methyl]tetrazine ([m]Tz)-modified macromers, leading to the first group of synthetic iEDDA click hydrogels with highly tunable hydrolytic degradation kinetics. We further exploited Tz and mTz dual conjugation to achieve tunable hydrolytic degradation with an in vitro degradation time ranging from 2 weeks to 3 months. Finally, we demonstrated the excellent in vitro cytocompatibility and in vivo biocompatibility of the new injectable PEGNBCA-based iEDDA click cross-linked hydrogels.

| S-EPMC9554872 | biostudies-literature

Hyperconjugative Antiaromaticity Activates 4H-Pyrazoles as Inverse-Electron-Demand Diels-Alder Dienes.

Project description:The Diels-Alder reactivity of 4,4-difluoro-3,5-diphenyl-4H-pyrazole was investigated experimentally and computationally with endo-bicyclo[6.1.0]non-4-yne. The computationally predicted rate enhancement from hyperconjugative antiaromaticity induced by fluorination of cyclopentadienes at the 5-position extends to five-membered heterocyclic dienes containing a saturated center. 4,4-Difluoro-4H-pyrazoles are new electron-deficient dienes with rapid reactivities toward strained alkynes.

| S-EPMC7015664 | biostudies-literature

Scope of the inverse electron demand Diels-Alder reactions of 1,2,3-triazine.

Project description:An examination of the scope of the inverse electron demand Diels-Alder reactions of the parent unsubstituted 1,2,3-triazine is described including the first report of its unique capabilities for participating in previously unexplored [4 + 2] cycloaddition reactions with heterodienophiles.

| S-EPMC3093666 | biostudies-literature

Tetrazine ligation: fast bioconjugation based on inverse-electron-demand Diels-Alder reactivity.

Project description:Described is a bioorthogonal reaction that proceeds with unusually fast reaction rates without need for catalysis: the cycloaddition of s-tetrazine and trans-cyclooctene derivatives. The reactions tolerate a broad range of functionality and proceed in high yield in organic solvents, water, cell media, or cell lysate. The rate of the ligation between trans-cyclooctene and 3,6-di-(2-pyridyl)-s-tetrazine is very rapid (k2 2000 M-1 s-1). This fast reactivity enables protein modification at low concentration.

| S-EPMC2653060 | biostudies-literature

Specific Binding of Liposomal Nanoparticles through Inverse Electron-Demand Diels-Alder Click Chemistry.

Project description:Here, we report a method to specifically bind liposomal radiopharmaceuticals to a CoCrMo alloy, which can be used in arterial stents, via an irreversible inverse electron-demand Diels-Alder reaction. Inspired by recent accomplishments in pre-targeted imaging using tetrazine-trans-cyclooctene click chemistry, we synthesized 89Zr-labeled trans-cyclooctene-functionalized liposomal nanoparticles, which were validated on a tetrazine-appended polydopamine-coated CoCrMo surface. In efforts to ultimately translate this new material to biomedical applications, we compared the ability of 89Zr-TCO-liposomal nanoparticles (89Zr-TCO-LNP) to be immobilized on the tetrazine surface to the control suspensions of non-TCO functionalized 89Zr-liposomal nanoparticles. Ultimately, this platform technology could result in a systemic decrease of the radiotherapeutic dose deposited in non-targeted tissues by specific removal of long-circulating liposomal radiopharmaceuticals from the blood pool.

| S-EPMC5641912 | biostudies-literature

Orthogonal Catalysis for an Enantioselective Domino Inverse-Electron Demand Diels-Alder/Substitution Reaction.

Project description:An enantioselective domino process for the synthesis of substituted 1,2-dihydronaphthalenes has been developed by the combination of chiral amines and a bidentate Lewis acid in an orthogonal catalysis. This new method is based on an inverse electron-demand Diels-Alder and a subsequent group exchange reaction. An enamine is generated in situ from an aldehyde and a chiral secondary amine catalyst that reacts with phthalazine, activated by the coordination to a bidentate Lewis acid catalyst. The absolute configuration of the product is controlled by chiral information provided by the amine. The formed ortho-quinodimethane intermediate is then transformed via a group exchange reaction with thiols. The new method shows a broad scope and tolerates a wide range of functional groups with enantiomeric ratios up to 91 : 9. All-in-all, this enantioselective synthesis tool provides an easy access to complex 1,2-dihydronaphthalenes starting from readily available phthalazine, aldehydes and thiols in a combinatorial way.

| S-EPMC9299787 | biostudies-literature

Inverse electron demand Diels-Alder click chemistry for pretargeted PET imaging and radioimmunotherapy.

Project description:Radiolabeled antibodies have shown promise as tools for both the nuclear imaging and endoradiotherapy of cancer, but the protracted circulation time of radioimmunoconjugates can lead to high radiation doses to healthy tissues. To circumvent this issue, we have developed an approach to positron emission tomography (PET) imaging and radioimmunotherapy (RIT) predicated on radiolabeling the antibody after it has reached its target within the body. This in vivo pretargeting strategy is based on the rapid and bio-orthogonal inverse electron demand Diels-Alder reaction between tetrazine (Tz) and trans-cyclooctene (TCO). Pretargeted PET imaging and RIT using TCO-modified antibodies in conjunction with Tz-bearing radioligands produce high activity concentrations in target tissues as well as reduced radiation doses to healthy organs compared to directly labeled radioimmunoconjugates. Herein, we describe how to prepare a TCO-modified antibody (humanized A33-TCO) as well as how to synthesize two Tz-bearing radioligands: one labeled with the positron-emitting radiometal copper-64 ([64Cu]Cu-SarAr-Tz) and one labeled with the β-emitting radiolanthanide lutetium-177 ([177Lu]Lu-DOTA-PEG7-Tz). We also provide a detailed description of pretargeted PET and pretargeted RIT experiments in a murine model of human colorectal carcinoma. Proper training in both radiation safety and the handling of laboratory mice is required for the successful execution of this protocol.

| S-EPMC8917728 | biostudies-literature

Enzyme-Catalyzed Inverse-Electron Demand Diels-Alder Reaction in the Biosynthesis of Antifungal Ilicicolin H.

Project description:The pericyclases are a growing superfamily of enzymes that catalyze pericyclic reactions. We report a pericyclase IccD catalyzing an inverse-electron demand Diels-Alder (IEDDA) reaction with a rate acceleration of 3 × 105-fold in the biosynthesis of fungal natural product ilicicolin H. We demonstrate IccD is highly periselective toward the IEDDA cycloaddition over a competing normal electron demand Diels-Alder (NEDDA) reaction from an ambimodal transition state. A predicted flavoenzyme IccE was identified to epimerize the IEDDA product 8- epi-ilicicolin H to ilicicolin H, a step that is critical for the observed antifungal activity of ilicicolin H. Our results reveal the ilicicolin H biosynthetic pathway and add to the collection of pericyclic reactions that are catalyzed by pericyclases.

| S-EPMC6585442 | 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