Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

N-aryl lactams by regioselective ozonation of N-aryl cyclic amines.

ABSTRACT: Ozonation of N-aryl-cyclic amines in organic solvents gave N-aryl-lactams regioselectively. In particular, 4-(4-aminophenyl)-morpolin-3-one, a key intermediate in the preparation of factor Xa inhibitors, was obtained in fair yields. The method represents an alternative approach for the lactamization of tertiary N-arylic substrates and is based on a "metal-free" introduction of the carbonyl function into the heterocyclic ring.

SUBMITTER: Saliu F

PROVIDER: S-EPMC3767345 | biostudies-literature | 2012

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

N-aryl lactams by regioselective ozonation of N-aryl cyclic amines.

Saliu Francesco F Orlandi Marco M Bruschi Maurizio M

ISRN organic chemistry 20120918

Ozonation of N-aryl-cyclic amines in organic solvents gave N-aryl-lactams regioselectively. In particular, 4-(4-aminophenyl)-morpolin-3-one, a key intermediate in the preparation of factor Xa inhibitors, was obtained in fair yields. The method represents an alternative approach for the lactamization of tertiary N-arylic substrates and is based on a "metal-free" introduction of the carbonyl function into the heterocyclic ring. ...[more]

PMID: 24052840

Similar Datasets

Regioselective, Photocatalytic α-Functionalization of Amines.

Project description:Photocatalytic α-functionalization of amines provides a mild and atom-economical means to synthesize α-branched amines. Prior examples featured symmetrical or electronically biased substrates. Here we report a controllable α-functionalization of amines in which regioselectivity can be tuned with minor changes to the reaction conditions.

| S-EPMC8475292 | biostudies-literature

Regioselective α-Cyanation of Unprotected Alicyclic Amines.

Project description:Secondary alicyclic amines are converted to α-aminonitriles via addition of TMSCN to their corresponding imines, intermediates that are produced in situ via the oxidation of amine-derived lithium amides with simple ketone oxidants. Amines with an existing α-substituent undergo regioselective α'-cyanation even if the C-H bonds at that site are less activated. Amine α-arylation can be combined with α'-cyanation to generate difunctionalized products in a single operation.

| S-EPMC9548390 | biostudies-literature

Deconstructive diversification of cyclic amines.

Project description:Deconstructive functionalization involves carbon-carbon (C-C) bond cleavage followed by bond construction on one or more of the constituent carbons. For example, ozonolysis1 and olefin metathesis2,3 have allowed each carbon in C=C double bonds to be viewed as a functional group. Despite the substantial advances in deconstructive functionalization involving the scission of C=C double bonds, there are very few methods that achieve C(sp3)-C(sp3) single-bond cleavage and functionalization, especially in relatively unstrained cyclic systems. Here we report a deconstructive strategy to transform saturated nitrogen heterocycles such as piperidines and pyrrolidines, which are important moieties in bioactive molecules, into halogen-containing acyclic amine derivatives through sequential C(sp3)-N and C(sp3)-C(sp3) single-bond cleavage followed by C(sp3)-halogen bond formation. The resulting acyclic haloamines are versatile intermediates that can be transformed into various structural motifs through substitution reactions. In this way we achieve the skeletal remodelling of cyclic amines, an example of scaffold hopping. We demonstrate this deconstructive strategy by the late-stage diversification of proline-containing peptides.

| S-EPMC6317721 | biostudies-literature

Asymmetric Redox-Annulation of Cyclic Amines.

Project description:Cyclic amines such as 1,2,3,4-tetrahydroisoquinoline undergo regiodivergent annulation reactions with 4-nitrobutyraldehydes. These redox-neutral transformations enable the asymmetric synthesis of highly substituted polycyclic ring systems in just two steps from commercial materials. The utility of this process is illustrated in a rapid synthesis of (-)-protoemetinol. Computational studies provide mechanistic insights and implicate the elimination of acetic acid from an ammonium nitronate intermediate as the rate-determining step.

| S-EPMC4599696 | biostudies-literature

Facile Conversion of Aryl Amines Having No α-Methylene to Aryl Nitriles.

Project description:Dimethyl carbonimidodithioates, 2 derived from various primary aryl amines (1) by reacting with carbon disulfide and methyl iodide in dimethyl formamide in the presence of concentrated sodium hydroxide, are converted to the diaziridine derivatives, 3 by reacting with hydrazine in ethanol. The diaziridines, 3 on oxidation with lead tetraacetate in refluxing xylene, extrudes nitrogen, and intramolecular stabilization, particularly 1,2-carbon migration, takes place to give the product, 5. The reaction may take place through the intermediates, diazirines, 4, which have not been isolated. This work provides a new approach for the conversion of aryl amines having no α-methylene to aryl nitriles.

| S-EPMC9453805 | biostudies-literature

Ozonation of Decalin as a Model Saturated Cyclic Molecule: A Spectroscopic Study.

Project description:Ozonolysis is used for oxidation of a model cyclic molecule-decalin, which may be considered as an analog of saturated cyclic molecules present in heavy oil. The conversion of decalin exceeds 50% with the highest yield of formation of acids about 15-17%. Carboxylic acids, ketones/aldehydes, and alcohols are produced as intermediate products. The methods of UV-visible, transmission IR, attenuated total reflection IR-spectroscopy, NMR and mass-spectrometry were used to identify reaction products and unravel a possible reaction mechanism. The key stage of the process is undoubtedly the activation of the first C-H bond and the formation of peroxide radicals.

| S-EPMC8469405 | biostudies-literature

Redox-Annulation of Cyclic Amines and ?-Ketoaldehydes.

Project description:Benzo[a]quinolizine-2-one derivatives are readily assembled from 1,2,3,4-tetrahydroisoquinoline and ?-ketoaldehydes by means of a new intramolecular redox-Mannich process. These reactions are promoted by simple acetic acid and are thought to involve azomethine ylides as reactive intermediates.

| S-EPMC4782176 | biostudies-literature

Polymer-Supported-Cobalt-Catalyzed Regioselective Cyclotrimerization of Aryl Alkynes.

Project description:A convoluted poly(4-vinylpyridine) cobalt(II) (P4VP-CoCl2) system was developed as a stable and reusable heterogeneous catalyst. The local structure near the Co atom was determined on the basis of experimental data and theoretical calculations. This immobilized cobalt catalyst showed high selectivity and catalytic activity in the [2 + 2 + 2] cyclotrimerization of terminal aryl alkynes. With 0.033 mol % P4VP-CoCl2, the regioselective formation of 1,3,5-triarylbenzene was realized without 1,2,4-triarylbenzene formation. Further, a multigram-scale (11 g) reaction proceeded efficiently. In addition, the polymer-supported catalyst was successfully recovered and used three times. X-ray photoelectron spectroscopy analysis of the recovered catalyst suggested that cobalt was in the +2 oxidation state. The 1,3,5-triarylbenzene derivatives were applied to the synthesis of a molecular beam electron resist and a polycyclic aromatic hydrocarbon.

| S-EPMC8611791 | biostudies-literature

Structural characterization of N-protonated amides: regioselective N-activation of medium-bridged twisted lactams.

Project description:The straightforward protonation of lactams by treatment with acid and the full structural characterization of three resulting N-protonated lactams are disclosed. This work provides experimental evidence that N-protonation of amide bonds results in a dramatic increase in nonplanarity about the C-N amide bond. The resulting compounds are discussed in structural, spectroscopic, and reactivity terms. The data suggest that distortion of these amide bonds by approximately 50 degrees is sufficient for their effective N-activation.

| S-EPMC2920036 | biostudies-literature

Redox-neutral α,β-difunctionalization of cyclic amines.

Project description:In contrast to the continuously growing number of methods that allow for the efficient α-functionalization of amines, few strategies exist that enable the direct functionalization of amines in the β-position. A general redox-neutral strategy is outlined for amine β-functionalization and α,β-difunctionalization that utilizes enamines generated in situ. This concept is demonstrated in the context of preparing polycyclic N,O-acetals from simple 1-(aminomethyl)-β-naphthols and 2-(aminomethyl)-phenols.

| S-EPMC4068263 | 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