Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Diastereoselective synthesis of nitroso acetals from (S,E)-?-aminated nitroalkenes via multicomponent [4 + 2]/[3 + 2] cycloadditions promoted by LiCl or LiClO4.

ABSTRACT: Chiral nonracemic aminated nitroso acetals were synthesized via diastereoselective multicomponent [4 + 2]/[3 + 2] cycloadditions employing new (S,E)-?-nitrogenated nitroalkenes 5a-c as heterodienes, ethyl vinyl ether (EVE) as a dienophile, and selected electron-deficient alkenes as 1,3-dipolarophiles. The employment of different organic solutions of LiClO4 or LiCl as promoter systems provided the respective nitroso acetals with yields from 34-72% and good levels of diastereoselectivity. In addition, the nitroso acetal 9c was transformed to the pyrrolizidin-3-one derivative 14c, proving the usefulness of the route in the synthesis of an interesting chiral compound. The elucidation of the stereostructures was based on 2D COSY, NOESY and HSQC NMR experiments as well as an X-ray diffraction experiment.

SUBMITTER: de Carvalho LL

PROVIDER: S-EPMC3678848 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Diastereoselective synthesis of nitroso acetals from (S,E)-γ-aminated nitroalkenes via multicomponent [4 + 2]/[3 + 2] cycloadditions promoted by LiCl or LiClO4.

de Carvalho Leandro Lara LL Burrow Robert Alan RA Pereira Vera Lúcia Patrocinio VL

Beilstein journal of organic chemistry 20130430

Chiral nonracemic aminated nitroso acetals were synthesized via diastereoselective multicomponent [4 + 2]/[3 + 2] cycloadditions employing new (S,E)-γ-nitrogenated nitroalkenes 5a-c as heterodienes, ethyl vinyl ether (EVE) as a dienophile, and selected electron-deficient alkenes as 1,3-dipolarophiles. The employment of different organic solutions of LiClO4 or LiCl as promoter systems provided the respective nitroso acetals with yields from 34-72% and good levels of diastereoselectivity. In addit ...[more]

PMID: 23766798

Similar Datasets

Asymmetric multicomponent reactions: diastereoselective synthesis of substituted pyrrolidines and prolines.

Project description:A novel diastereoselective synthesis of substituted pyrrolidines has been developed. Asymmetric multicomponent reactions of optically active phenyldihydrofuran, N-tosyl imino ester, and silane reagents in a one-pot operation afforded highly substituted pyrrolidine derivatives diastereoselectively. The reaction is quite efficient and constructed up to three stereogenic centers in a single operation.

| S-EPMC3179855 | biostudies-literature

Highly diastereoselective synthesis of modified nucleosides via an asymmetric multicomponent reaction.

Project description:We have developed a practical synthesis of unique nucleoside derivatives via TiCl(4) promoted multicomponent reaction of optically active dihydrofuran, ethyl pyruvate/glyoxylate, and a TMS protected nucleobase in a single-pot operation.

| S-EPMC6037177 | biostudies-literature

Diastereoselective Synthesis of Cyclopenta[c]furans by a Catalytic Multicomponent Reaction.

Project description:A diastereoselective three-component reaction between alkynyl enones, aldehydes and secondary amines is reported. With the aid of a benign indium catalyst, a range of highly substituted cyclopenta[c]furan derivatives can be obtained in a single-step procedure. The formation of the stereodefined heterocyclic motifs takes place via in situ generation of enamines followed by two sequential cyclization steps.

| S-EPMC5113805 | biostudies-literature

Enantioselective palladium-catalyzed [3 + 2] cycloadditions of trimethylenemethane with nitroalkenes.

Project description:Nitroalkenes readily undergo palladium-catalyzed [3 + 2] cycloaddition with trimethylenemethane to generate nitrocyclopentanes in excellent yield and enantioselectivity. Furthermore, the products thus formed are highly versatile synthetic intermediates and provide convenient access to both cyclopentylamines and cyclopentenones.

| S-EPMC3268375 | biostudies-literature

Diastereoselective pyrrolidine synthesis via copper promoted intramolecular aminooxygenation of alkenes: formal synthesis of (+)-monomorine.

Project description:The diastereoselectivity of the copper-promoted intramolecular aminooxygenation of various alkene substrates was investigated. Alpha-substituted 4-pentenyl sulfonamides favor the formation of 2,5-cis-pyrrolidines (dr >20:1) giving excellent yields which range from 76-97% while gamma-substituted substrates favor the 2,3-trans pyrrolidine adducts with moderate selectivity (ca. 3:1). A substrate whose N-substituent was directly tethered to the alpha-carbon exclusively yielded the 2,5-trans pyrrolidine. The synthetic utility of the method was demonstrated by a short and efficient formal synthesis of (+)-monomorine.

| S-EPMC2714983 | biostudies-literature

Tandem 6pi-electrocyclization and cycloaddition of nitrodienes to yield multicyclic nitroso acetals.

Project description:Upon heating, nitrodienes rearrange through 6pi-electrocyclization to form nitronate intermediates, which can be captured through tandem [3 + 2] dipolar cycloadditions to form highly functionalized nitroso acetals. The one-pot, two-step domino process is highly efficient, proceeding with good facial selectivity and exoselectivity. Dipolarophiles featuring electron-rich, -neutral, and -deficient carbon-carbon double bonds are viable substrates for [3 + 2] cycloadditions with the in situ generated nitronates. In addition, the highly functionalized nitroso acetal products can be hydrogenolyzed selectively to form densely functionalized spirocyclic hydroxy amides or hydroxy gamma-amino acids.

| S-EPMC2903206 | biostudies-literature

Fluorogenic Strain-Promoted Alkyne-Diazo Cycloadditions.

Project description:Fluorogenic reactions, in which non- or weakly fluorescent reagents produce highly fluorescent products, are attractive for detecting a broad range of compounds in the fields of bioconjugation and material sciences. Herein, we report that a dibenzocyclooctyne derivative modified with a cyclopropenone moiety (Fl-DIBO) can undergo fast strain-promoted cycloaddition reactions under catalyst-free conditions with azides, nitrones, nitrile oxides, as well as mono- and disubstituted diazo-derivatives. Although the reaction with nitrile oxides, nitrones, and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H-pyrazole derivatives that exhibited an approximately 160-fold fluorescence enhancement over Fl-DIBO combined with a greater than 10,000-fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H-pyrazoles, which are formed by reaction with disubstituted diazo-derivatives, is likely due to the presence of energetically low-lying (n,π*) states. The fluorogenic probe Fl-DIBO was successfully employed for the labeling of diazo-tagged proteins without detectable background signal. Diazo-derivatives are emerging as attractive reporters for the labeling of biomolecules, and the studies presented herein demonstrate that Fl-DIBO can be employed for visualizing such biomolecules without the need for probe washout.

| S-EPMC4712747 | biostudies-literature

An Efficient Synthesis of Oxygen-Bridged Spirooxindoles via Microwave-Promoted Multicomponent Reaction.

Project description:A microwave-promoted multicomponent reaction of isatins, α-amino acids and 1,4-dihydro-1,4-epoxynaphthalene is achieved under environmentally friendly conditions, delivering oxygen-bridged spirooxindoles within 15 min in good to excellent yields. The attractive features of the 1,3-dipolar cycloaddition are the compatibility of various primary amino acids and the high efficiency of the short reaction time. Moreover, the scale-up reaction and synthetic transformations of spiropyrrolidine oxindole further demonstrate its synthetic utility. This work provides powerful means to expand the structural diversity of spirooxindole as a promising scaffold for novel drug discovery.

| S-EPMC10146779 | biostudies-literature

Highly regio- and stereoselective Diels-Alder cycloadditions via two-step and multicomponent reactions promoted by infrared irradiation under solvent-free conditions.

Project description:Infrared irradiation promoted the Diels-Alder cycloadditions of exo-2-oxazolidinone dienes 1-3 with the Knoevenagel adducts 4-6, as dienophiles, leading to the synthesis of new 3,5-diphenyltetrahydrobenzo[d]oxazol-2-one derivatives (7, 9, 11 and 13-17), under solvent-free conditions. These cycloadditions were performed with good regio- and stereoselectivity, favoring the para-endo cycloadducts. We also evaluated the one-pot three-component reaction of active methylene compounds 20, benzaldehydes 21 and exo-2-oxazolidinone diene 2 under the same reaction conditions. A cascade Knoevenagel condensation/Diels-Alder cycloaddition reaction was observed, resulting in the final adducts 13-16 in similar yields. These procedures are environmentally benign, because no solvent and no catalyst were employed in these processes. The regioselectivity of these reactions was rationalized by Frontier Molecular Orbital (FMO) calculations.

| S-EPMC3317676 | biostudies-literature

Intracellular Ruthenium-Promoted (2+2+2) Cycloadditions.

Project description:Metal-mediated intracellular reactions are becoming invaluable tools in chemical and cell biology, and hold promise for strongly impacting the field of biomedicine. Most of the reactions reported so far involve either uncaging or redox processes. Demonstrated here for the first time is the viability of performing multicomponent alkyne cycloaromatizations inside live mammalian cells using ruthenium catalysts. Both fully intramolecular and intermolecular cycloadditions of diynes with alkynes are feasible, the latter providing an intracellular synthesis of appealing anthraquinones. The power of the approach is further demonstrated by generating anthraquinone AIEgens (AIE=aggregation induced emission) that otherwise do not go inside cells, and by modifying the intracellular distribution of the products by simply varying the type of ruthenium complex.

| S-EPMC7689831 | 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