Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Ring Opening Reactions of β-Propiolactam in Superacidic Media.

ABSTRACT: The reaction of β-propiolactam in the superacidic systems HF/MF₅ (M=Sb, As) led to the formation of monoprotonated 3-aminopropanoyl fluoride in the form of [C(O)F(CH₂ )₂ NH₃ ][SbF₆ ] and [C(O)F(CH₂ )₂ NH₃ ][AsF₆ ]. In the presence of traces of water, the diprotonated species β-alanine [C(OH)₂ (CH₂ )₂ NH₃ ][AsF₆ ]₂ was synthesized for the first time. All salts were characterized by low-temperature infrared and Raman spectroscopy. Additionally, single-crystal X-ray analyses were conducted in the case of [C(O)F(CH₂ )₂ NH₃ ][SbF₆ ] and [C(OH)₂ (CH₂ )₂ NH₃ ][AsF₆ ]₂ . By using SO₂ instead of HF as the solvent, the salt [C(OH)₂ (CH₂ )₂ NHSO][SbF₆ ]₂ was obtained, and single-crystal X-ray analysis of this salt containing a thionylimide moiety was conducted. For the formation of these open-chain compounds, an acyl cationic species as intermediate is assumed, which is formed from N-protonated β-propiolactam. Quantum chemical calculations at the B3LYP/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels of theory were carried out to gain a better understanding of the formation and the structural properties of protonated β-propiolactam.

SUBMITTER: Beck S

PROVIDER: S-EPMC9302645 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Alkylative Aziridine Ring-Opening Reactions.

Project description:In this study, the highly strained three-membered aziridine ring was successfully activated as the aziridinium ion by alkylation of the ring nitrogen with a methyl, ethyl or allyl group, which was followed by ring opening with external nucleophiles such as acetate and azide. Such alkylative aziridine ring opening provides an easy route for the synthesis of various N-alkylated amine-containing molecules with concomitant introduction of an external nucleophile at either its α- or β-position.

| S-EPMC8003214 | biostudies-literature

Ring-opening and ring-expansion reactions of carborane-fused borirane.

Project description:Though the reaction chemistry of three-membered ring molecules such as cyclopropanes and their heteroatom-containing analogues has been extensively studied, the chemical properties of their boron analogues, boriranes, are little known thus far. This work describes the diverse reactivity patterns of carborane-fused borirane 2. This borirane engages in ring-opening reactions with different types of Lewis acids, such as BBr3, GeCl2, GaCl3, BH3(SMe2) and HBpin, affording a series of ring-opening products, in which M-X or B-H bonds add across the B-C(cage) bond of the three-membered ring in 2. On the other hand, borirane 2 can undergo ring-expansion reactions with unsaturated molecules such as PhCHO, CO2 and PhCN to give ring-expansion products, five-membered boracycles, via a concerted reaction mechanism as supported by DFT calculations. The results of this work not only enrich the reaction chemistry of boriranes, but also offer new routes to boron-containing compounds and heterocycles.

| S-EPMC8513813 | biostudies-literature

Flavin-enabled reductive and oxidative epoxide ring opening reactions.

Project description:Epoxide ring opening reactions are common and important in both biological processes and synthetic applications and can be catalyzed in a non-redox manner by epoxide hydrolases or reductively by oxidoreductases. Here we report that fluostatins (FSTs), a family of atypical angucyclines with a benzofluorene core, can undergo nonenzyme-catalyzed epoxide ring opening reactions in the presence of flavin adenine dinucleotide (FAD) and nicotinamide adenine dinucleotide (NADH). The 2,3-epoxide ring in FST C is shown to open reductively via a putative enol intermediate, or oxidatively via a peroxylated intermediate with molecular oxygen as the oxidant. These reactions lead to multiple products with different redox states that possess a single hydroxyl group at C-2, a 2,3-vicinal diol, a contracted five-membered A-ring, or an expanded seven-membered A-ring. Similar reactions also take place in both natural products and other organic compounds harboring an epoxide adjacent to a carbonyl group that is conjugated to an aromatic moiety. Our findings extend the repertoire of known flavin chemistry that may provide new and useful tools for organic synthesis.

| S-EPMC9391479 | biostudies-literature

Preparation and ring-opening reactions of N-diphenylphosphinyl vinyl aziridines.

Project description:Predominantly (E)-N-diphenylphosphinyl vinyl aziridines are prepared by a reaction of N-diphenylphosphinyl imines with ?-bromoallyllithium in the presence of freshly fused ZnCl2. These aziridines undergo a ring-opening reaction with a variety of carbon and heteronucleophiles, in good yield, and generally with good regioselectivity.

| S-EPMC3678660 | biostudies-literature

Revealing pseudorotation and ring-opening reactions in colloidal organic molecules.

Project description:Colloids have a rich history of being used as 'big atoms' mimicking real atoms to study crystallization, gelation and the glass transition of condensed matter. Emulating the dynamics of molecules, however, has remained elusive. Recent advances in colloid chemistry allow patchy particles to be synthesized with accurate control over shape, functionality and coordination number. Here, we show that colloidal alkanes, specifically colloidal cyclopentane, assembled from tetrameric patchy particles by critical Casimir forces undergo the same chemical transformations as their atomic counterparts, allowing their dynamics to be studied in real time. We directly observe transitions between chair and twist conformations in colloidal cyclopentane, and we elucidate the interplay of bond bending strain and entropy in the molecular transition states and ring-opening reactions. These results open the door to investigate complex molecular kinetics and molecular reactions in the high-temperature classical limit, in which the colloidal analogue becomes a good model.

| S-EPMC8121934 | biostudies-literature

Organocatalyzed ring-opening reactions of γ-carbonyl-substituted ε-caprolactones.

Project description:Side-chain-functionalized aliphatic polyesters are promising as functional biodegradable polymers. We have investigated ring-opening reactions of γ-carbonyl-substituted ε-caprolactones (gCCLs) to obtain poly(ε-caprolactone) (PCL) analogues. Organic catalysts and Sn(Oct)2 often used for the ring-opening polymerization (ROP) of ε-caprolactone (CL) have been explored to find the conditions for the formation of polymeric products of gCCLs. We confirmed the consumption of gCCLs in all catalyzed reactions. However, chain propagation hardly occurs, as the propagating species are preferentially transformed to α-substituted five-membered lactones when the substituents are linked by ester or not sterically hindered. Intramolecular cyclization to form thermodynamically stable five-membered lactones releases alcohols and amines, serving as nucleophiles for the subsequent ring opening of other gCCLs. Thus, apparent chain reactions are realized for continuous consumption of gCCLs. The reaction preference remains unchanged independent of the catalysts, although the reactions of the amide-linked gCCLs by acidic catalysts are slightly mitigated. Finally, copolymerization of CL and a gCCL catalyzed by diphenyl phosphate has been investigated, which enables the chain propagation reaction to yield the linear oligomers of PCL analogues containing up to 16 mol% of gCCL units. This study contributes to understanding the chemistry of ring-opening reactions of substituted lactones for designing functional degradable polymers.

| S-EPMC10507672 | biostudies-literature

Ring closing and opening reactions leading to aza-polycyclic aromatic compounds.

Project description:A series of functionalized aza-polycyclic aromatic compounds were prepared by a superacid-promoted ring closing and opening reaction cascade. A reaction mechanism is proposed, which involves reactive dicationic intermediates. A key step in the conversions involves ipso protonation of an aryl group and elimination of an alkyl phenyl group.

| S-EPMC3797622 | biostudies-literature

Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene with alcohols.

Project description:Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene derivatives using alcohol nucleophiles were investigated. The optimal conditions were found to be 10 mol % PdCl2(CH3CN)2 in methanol, offering yields up to 92%. The reaction was successful using primary, secondary and tertiary alcohol nucleophiles and was compatible with a variety of substituents on cyclopropanated oxabenzonorbornadiene. With unsymmetrical C1-substituted cyclopropanated 7-oxabenzonorbornadienes, the regioselectivity of the reaction was excellent, forming only one regioisomer in all cases.

| S-EPMC5082584 | biostudies-literature

Asymmetric ring-opening reactions of donor-acceptor cyclopropanes with 1,3-cyclodiones.

Project description:Asymmetric ring-opening reactions of donor-acceptor cyclopropanes with 1,3-cyclodiones have been established for the synthesis of enantioenriched γ-hydroxybutyric acid derivatives in the presence of Cu(ii)/trisoxazoline catalyst. These reactions offered the desired products in 70% to 93% yields with 79% to 99% enantiomeric excesses.

| S-EPMC9990749 | biostudies-literature

Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions.

Project description:Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene synthons. Here, we show that naphthalene epoxides generated by fungal peroxygenases can be subjected to nucleophilic ring opening, yielding non-racemic trans-disubstituted cyclohexadiene derivates, which in turn can be used for further chemical transformations. This approach may represent a promising shortcut for the synthesis of natural products and APIs.

| S-EPMC7976598 | 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