Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Using TOF-SIMS Spectrometry to Study the Kinetics of the Interfacial Retro Diels-Alder Reaction.

ABSTRACT: In this work, the use of Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) was explored as a technique for monitoring the interfacial retro Diels-Alder (retro DA) reaction occurring on well-controlled self-assembled monolayers (SAMs). A molecule containing a Diels-Alder (DA) adduct was grafted on to the monolayers, then the surface was heated at different temperatures to follow the reaction conversion. A TOF-SIMS analysis of the surface allowed the detection of a fragment from the molecule, which is released from the surface when retro DA reaction occurs. Hence, by monitoring the decay of this fragment's peak integral, the reaction conversion could be determined in function of the time and for different temperatures. The viability of this method was then discussed in comparison with the results obtained by ¹H NMR spectroscopy.

SUBMITTER: Hassouna L

PROVIDER: S-EPMC8161361 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Self-assembly using a retro Diels-Alder reaction.

Project description:Despite their great utility in synthetic and materials chemistry, Diels-Alder (DA) and retro Diels-Alder (rDA) reactions have been vastly unexplored in promoting self-assembly processes. Herein we describe the first example of a retro Diels-Alder (rDA) reaction-triggered self-assembly method. Release of the steric bulkiness associated with the bridged bicyclic DA adduct by the rDA reaction allowed generation of two building blocks that spontaneously self-assembled to form a supramolecular polymer. By employing photopolymerizable lipid building blocks, we demonstrated the efficiency of the rDA-based self-assembly strategy. Generation of reactive functional groups (maleimide and furan) that can be used for further modification of the supramolecular polymer is an additional meritorious feature of the rDA-based approach. Advantage was taken of reactive functional groups to fabricate stimulus-responsive selective and tunable colorimetric sensors. The strategy developed in this study should be useful for the design of systems that participate in triggered molecular assembly.

| S-EPMC8270933 | 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

C(alkyl)-C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction.

Project description:Activation and cleavage of carbon-carbon (C-C) bonds is a fundamental transformation in organic chemistry while inert C-C bonds cleavage remains a long-standing challenge. Retro-Diels-Alder (retro-DA) reaction is a well-known and important tool for C-C bonds cleavage but less been explored in methodology by contrast to other strategies. Herein, we report a selective C(alkyl)-C(vinyl) bond cleavage strategy realized through the transient directing group mediated retro-Diels-Alder reaction of a six-membered palladacycle, which is obtained from an in situ generated hydrazone and palladium hydride species. This unprecedented strategy exhibits good tolerances and thus offers new opportunities for late-stage modifications of complex molecules. DFT calculations revealed that an intriguing retro-Pd(IV)-Diels-Alder process is possibly involved in the catalytic cycle, thus bridging both Retro-Diels-Alder reaction and C-C bond cleavage. We anticipate that this strategy should prove instrumental for potential applications to achieve the modification of functional organic skeletons in synthetic chemistry and other fields involving in molecular editing.

| S-EPMC10160084 | biostudies-literature

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

Biosynthesis of Grandione: An Example of Tandem Hetero Diels-Alder/Retro-Claisen Rearrangement Reaction?

Project description:Mechanistic theoretical studies about the feasibility of the traditional proposed mechanism of formation for icetexane diterpene dimer grandione were assessed using density functional method at the M06-2X/6-31G(d,p) level of theory. Bulk water solvent effects were taken into account implicitly using the polarizable continuum model (SCI-PCM). The results were compared with the selectivity found in the biomimetic synthesis performed by experimental research groups. The relative free energy calculation shows that the one-step H-DA formation mechanism nominated in the literature is not a viable mechanism. We found that an alternative competing Tandem pathway is consistent with the experimental trends. Thus, our results suggested that the compound grandione is formed via a H-DA/retro-Claisen rearrangement and not by the traditional H-DA mechanism proposed early in the experimental studies. The H-DA initial step produce a biecyclic adduct followed by a domino retro-Claisen rearrangement that releases the energy strain of the bicyclic intermediary. Steric issues and hyperconjugation interactions are the mainly factors driving the reaction nature and the selectivity in the formation reaction. Finally, the enzymatic assistance for dimer formation was analyzed in terms of the calculated transition state energy barrier.

| S-EPMC6222908 | biostudies-other

Continuous-flow retro-Diels-Alder reaction: an efficient method for the preparation of pyrimidinone derivatives.

Project description:The syntheses of various pyrimidinones as potentially bioactive products by means of the highly controlled continuous-flow retro-Diels-Alder reaction of condensed pyrimidinone derivatives are presented. Noteworthy, the use of this approach allowed us to rapidly screen a selection of conditions and quickly confirm the viability of preparing the desired pyrimidinones in short reaction times. Yields typically higher than those published earlier using conventional batch or microwave processes were achieved.

| S-EPMC5815275 | biostudies-literature

Himic Anhydride: A Retro Diels-Alder Reaction for the Organic Laboratory and an Accompanying NMR Study.

Project description:The thermal equilibration of himic anhydride [IUPAC (2-endo,3-endo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride] to (2-exo,3-exo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride and subsequent recrystallization of the exo-product can be performed as a standard undergraduate laboratory experiment requiring minimal equipment. The interpretation of the 1H NMR spectra for these norbornene carboxylic anhydride molecules promotes an appreciation of constrained ring systems and factors that affect chemical shifts and coupling constants.

| S-EPMC8675133 | biostudies-literature

The pentadehydro-Diels-Alder reaction.

Project description:In the classic Diels-Alder [4?+?2] cycloaddition reaction, the overall degree of unsaturation (or oxidation state) of the 4? (diene) and 2? (dienophile) pairs of reactants dictates the oxidation state of the newly formed six-membered carbocycle. For example, in the classic Diels-Alder reaction, butadiene and ethylene combine to produce cyclohexene. More recent developments include variants in which the number of hydrogen atoms in the reactant pair and in the resulting product is reduced by, for example, four in the tetradehydro-Diels-Alder (TDDA) and by six in the hexadehydro-Diels-Alder (HDDA) reactions. Any oxidation state higher than tetradehydro (that is, lacking more than four hydrogens) leads to the production of a reactive intermediate that is more highly oxidized than benzene. This increases the power of the overall process substantially, because trapping of the reactive intermediate can be used to increase the structural complexity of the final product in a controllable and versatile manner. Here we report an unprecedented overall 4??+?2? cycloaddition reaction that generates a different, highly reactive intermediate known as an ?,3-dehydrotoluene. This species is in the same oxidation state as a benzyne. Like benzynes, ?,3-dehydrotoluenes can be captured by various trapping agents to produce structurally diverse products that are complementary to those arising from the HDDA process. We call this new cycloisomerization process a pentadehydro-Diels-Alder (PDDA) reaction-a nomenclature chosen for chemical taxonomic reasons rather than mechanistic ones. In addition to alkynes, nitriles (RC?N), although non-participants in aza-HDDA reactions, readily function as the 2? component in PDDA cyclizations to produce, via trapping of the ?,3-(5-aza)dehydrotoluene intermediates, pyridine-containing products.

| S-EPMC4877333 | biostudies-literature

Photochemical Hexadehydro-Diels-Alder Reaction.

Project description:We demonstrate that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction to produce reactive benzyne derivatives can be initiated photochemically. As with the thermal variant of the HDDA process, the reactive intermediates are formed in the absence of reagents or the resulting byproducts required for the generation of benzynes by traditional methods. This photo-HDDA (or hν-HDDA) reaction occurs at much lower temperatures (including even at -70 °C) than the thermal HDDA, but the benzynes produced behave in the same fashion with respect to their trapping reactions, suggesting they are of the same electronic state.

| S-EPMC6348472 | biostudies-literature

The hexadehydro-Diels-Alder reaction.

Project description:Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.

| S-EPMC3538845 | 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