Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Pd-catalyzed Semmler-Wolff reactions for the conversion of substituted cyclohexenone oximes to primary anilines.

ABSTRACT: Homogeneous Pd catalysts have been identified for the conversion of cyclohexenone and tetralone O-pivaloyl oximes to the corresponding primary anilines and 1-aminonaphthalenes. This method is inspired by the Semmler-Wolff reaction, a classic method that exhibits limited synthetic utility owing to its forcing conditions, narrow scope, and low product yields. The oxime N-O bond undergoes oxidative addition to Pd(0)(PCy3)2, and the product of this step has been characterized by X-ray crystallography and shown to undergo dehydrogenation to afford the aniline product.

SUBMITTER: Hong WP

PROVIDER: S-EPMC3826266 | biostudies-literature | 2013 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Pd-catalyzed Semmler-Wolff reactions for the conversion of substituted cyclohexenone oximes to primary anilines.

Hong Wan Pyo WP Iosub Andrei V AV Stahl Shannon S SS

Journal of the American Chemical Society 20130904 37

Homogeneous Pd catalysts have been identified for the conversion of cyclohexenone and tetralone O-pivaloyl oximes to the corresponding primary anilines and 1-aminonaphthalenes. This method is inspired by the Semmler-Wolff reaction, a classic method that exhibits limited synthetic utility owing to its forcing conditions, narrow scope, and low product yields. The oxime N-O bond undergoes oxidative addition to Pd(0)(PCy3)2, and the product of this step has been characterized by X-ray crystallograph ...[more]

PMID: 23987212

Similar Datasets

Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium.

Project description:Primary anilines are essential building blocks to synthesize various pharmaceuticals, agrochemicals, pigments, electronic materials, and others. To date, the syntheses of primary anilines mostly rely on the reduction of nitroarenes or the transition-metal-catalyzed Ullmann, Buchwald-Hartwig and Chan-Lam cross-coupling reactions with ammonia, in which non-renewable petroleum-based chemicals are typically used as feedstocks via multiple step syntheses. A long-standing scientific challenge is to synthesize various primary anilines directly from renewable sources. Herein, we report a general method to directly convert a broad range of phenols into the corresponding primary anilines with the cheap and widely available hydrazine as both amine and hydride sources with simple Pd/C as the catalyst.

| S-EPMC6509994 | biostudies-literature

Copper mediated C-H amination with oximes: en route to primary anilines.

Project description:Here we report an efficient Cu(i)-mediated C-H amination reaction with oximes as amino donors to introduce NH2 groups directly. Various strongly coordinating heterocycles including quinoline, pyrimidine, pyrazine, pyrazole and triazole were tolerated well. The potential utility was further demonstrated in a late-stage modification of telmisartan (an antagonist for the angiotensin II receptor).

| S-EPMC6001278 | biostudies-literature

Synthesis of substituted tetrahydroindoloisoquinoline derivatives via intramolecular Pd-catalyzed alkene carboamination reactions.

Project description:Intramolecular Pd-catalyzed alkene carboamination reactions of substituted 2-allyl-N-(2-bromobenzyl)anilines are described. The substrates for these reactions are generated in two steps from readily available 2-allylanilines and 2-bromobenzaldehyde derivatives. The transformations afford substituted tetrahydroindoloisoquinolines, an uncommon class of fused bicyclic heterocycles, in good yield. The mechanism of these transformations is described, and a model that accounts for the observed product stereochemistry is proposed.

| S-EPMC4011572 | biostudies-literature

Pd(II)-Catalyzed Fujiwara-Moritani Reactions for the Synthesis and Functionalization of Substituted Coumarins.

Project description:Highly substituted coumarins, privileged and versatile scaffolds for bioactive natural products and fluorescence imaging, are obtained via a Pd(II)-catalyzed direct C-H alkenylation reaction (Fujiwara-Moritani reaction), which has emerged as a powerful tool for the construction and functionalization of heterocyclic compounds because of its chemical versatility and its environmental advantages. Thus, a selective 6-endo cyclization led to 4-substituted coumarins in moderate yields. Selected examples have been further functionalized in C3 through a second intermolecular C-H alkenylation reaction to give coumarin-acrylate hybrids, whose fluorescence spectra have been measured.

| S-EPMC8581981 | biostudies-literature

Pd-Catalyzed Alkene Difunctionalization Reactions of Enolates for the Synthesis of Substituted Bicyclic Cyclopentanes.

Project description:Palladium-catalyzed alkene difunctionalization reactions between alkenes bearing tethered aryl or alkenyl triflates and enolate nucleophiles are described. The transformations form two C-C bonds, a ring, and up to two stereocenters, while producing substituted cyclopentane derivatives that contain appended carbonyl functionality. Products are formed with up to >20:1 diastereoselectivity, and formation of sterically congested bonds between quaternary carbon atoms is feasible.

| S-EPMC7886259 | biostudies-literature

Pd-Catalyzed Heck-Type Reactions of Allenes for Stereoselective Syntheses of Substituted 1,3-Dienes.

Project description:A highly stereoselective Pd-catalyzed Heck-type reaction of allenes in which the stereochemistry of both olefins is set simultaneously was developed. The ligand CyJohnPhos was crucial to achieving stereoselectivity, while minimizing isomerization of the starting material through hydropalladation. The stereodetermining factors were proposed to be A1,3 strain between the catalyst and allene substituent, which influences the σ-π-σ equilibrium of the coupled allene intermediate, as well as eclipsing interactions of R groups in the β-hydride elimination. Good functional group tolerance and stereoselectivities for formation of the Z,E isomer were demonstrated. The methodology was further expanded to include the regioselective formation of 2,4-dienoates and 2,4-dienamides with a variety of substitution patterns, albeit in reduced stereoselectivities favoring the E,E isomer. A plausible mechanism is proposed to account for the observed selectivities and substituent effects.

| S-EPMC8727505 | biostudies-literature

Chemical Conversion of Hardly Ionizable Rhenium Aryl Chlorocomplexes with p-Substituted Anilines.

Project description:Fast and selective analytical methods help to ensure the chemical identity and desired purity of the prepared complexes before their medical application, and play an indispensable role in clinical practice. Mass spectrometry, despite some limitations, is an integral part of these methods. In the context of mass spectrometry, specific problems arise with the low ionization efficiency of particular analytes. Chemical derivatization was used as one of the most effective methods to improve the analyte's response and separation characteristics. The Schotten-Baumann reaction was successfully adapted for the derivatization of ESI hardly ionizable Re(VII) bis(catechol) oxochlorocomplex. Various alkyl and halogen p-substituted anilines as possible derivatization agents were tested. Unlike the starting complex, the reaction products were easily ionizable in electrospray, providing structurally characteristic molecular and fragment anions. DFT computer modeling, which proposed significant conformation changes of prepared complexes within their deprotonation, proved to have a close link to MS spectra. High-resolution MS and MS/MS measurements complemented with collision-induced dissociation experiments for detailed specification of prepared complexes' fragmentation pathways were used. The specified fragmentation schemes were analogous for all studied derivatives, with an exception for [Re(O)(Cat)2PIPA].

| S-EPMC8201000 | biostudies-literature

I(III)-Catalyzed Oxidative Cyclization-Migration Tandem Reactions of Unactivated Anilines.

Project description:An I(III)-catalyzed oxidative cyclization-migration tandem reaction using Selectfluor as the oxidant was developed that converts unactivated anilines into 3H-indoles is reported herein. The reaction requires as little as 1 mol % of the iodocatalyst and is mild, tolerating pyridine and thiophene functional groups, and the dependence of the diastereoselectivity of the process on the identity of the iodoarene or iodoalkane precatalyst suggests that the catalyst is present for the stereochemical determining C-N bond forming step.

| S-EPMC8135073 | biostudies-literature

Pyrrole-2-carboxylic acid as a ligand for the Cu-catalyzed reactions of primary anilines with aryl halides.

Project description:Pyrrole 2-carboxylic acid (L5) was found to be an effective ligand for the Cu-catalyzed monoarylation of anilines with aryl iodides and bromides. Under the reported conditions (10% CuI/20% L5/DMSO/K3PO 4/80-100 degrees C/20-24 h), a variety of useful functional groups were tolerated, and moderate to good yields of the diaryl amine products were obtained.

| S-EPMC2582381 | biostudies-literature

Stereoselective synthesis of substituted 1,3-oxazolidines via Pd-catalyzed carboamination reactions of O-vinyl-1,2-amino alcohols.

Project description:The stereoselective synthesis of 2,4- and 2,5-disubstituted 1,3-oxazolidines is accomplished via Pd-catalyzed carboamination of O-vinyl-1,2-amino alcohol derivatives. The transformations generate cis-disubstituted products with good to excellent diastereoselectivity, and enantiomerically enriched substrates are converted without loss of optical purity. In addition to yielding synthetically useful products that are difficult to generate with existing methods, these transformations illustrate that electron-rich enol ethers are viable substrates for alkene carboamination processes.

| S-EPMC3163040 | 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