Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Direct Primary Amination of Alkylmetals with NH-Oxaziridine.

ABSTRACT: A method for the primary electrophilic amination of primary, secondary, and tertiary organometallic substrates from a bench-stable NH-oxaziridine reagent is described. This facile and highly chemoselective transformation occurs at ambient temperature and without transition metal catalysts or purification by column chromatography to provide alkylamine products in a single step. Density functional theory (DFT) calculations revealed that, despite the basicity of alkylmetals, the direct NH-transfer pathway is favored over proton and O-transfer.

SUBMITTER: Behnke NE

PROVIDER: S-EPMC7803087 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Direct Primary Amination of Alkylmetals with NH-Oxaziridine.

Behnke Nicole Erin NE Kielawa Russell R Kwon Doo-Hyun DH Ess Daniel H DH Kürti László L

Organic letters 20181210 24

A method for the primary electrophilic amination of primary, secondary, and tertiary organometallic substrates from a bench-stable NH-oxaziridine reagent is described. This facile and highly chemoselective transformation occurs at ambient temperature and without transition metal catalysts or purification by column chromatography to provide alkylamine products in a single step. Density functional theory (DFT) calculations revealed that, despite the basicity of alkylmetals, the direct NH-transfer ...[more]

PMID: 30525689

Similar Datasets

Oxaziridine-mediated intramolecular amination of sp(3)-hybridized C-H bonds.

Project description:We describe a new oxaziridine-mediated approach to the amination of sp(3)-hybridized C-H bonds. In the presence of a copper(II) catalyst, N-sulfonyl oxaziridines participate in efficient intramolecular cyclization reactions to afford a variety of piperidine and tetrahydroisoquinoline structures. The aminal intermediates provide a convenient functional handle for further elaboration of these structures, demonstrating the utility of this new methodology for the rapid construction of structurally complex nitrogen-containing heterocycles.

| S-EPMC2737076 | biostudies-literature

Direct Aryl C-H Amination with Primary Amines Using Organic Photoredox Catalysis.

Project description:The direct catalytic C-H amination of arenes is a powerful synthetic strategy with useful applications in pharmaceuticals, agrochemicals, and materials chemistry. Despite the advances in catalytic C-H functionalization, the use of aliphatic amine coupling partners is limited. Described herein is the construction of C-N bonds, using primary amines, by direct C-H functionalization with an acridinium photoredox catalyst under an aerobic atmosphere. A wide variety of primary amines, including amino acids and more complex amines are competent coupling partners. Various electron-rich aromatics and heteroaromatics are useful scaffolds in this reaction, as are complex, biologically active arenes. We also describe the ability to functionalize arenes that are not oxidized by an acridinium catalyst, such as benzene and toluene, thus supporting a reactive amine cation radical intermediate.

| S-EPMC5995118 | biostudies-literature

A Protocol for Direct Stereospecific Amination of Primary, Secondary, and Tertiary Alkylboronic Esters.

Project description:The direct, stereospecific amination of alkylboronic and borinic esters can be conducted by treatment of the organoboron compound with methoxyamine and potassium tert-butoxide. In addition to being stereospecific, this process also enables the direct amination of tertiary boronic esters in an efficient fashion.

| S-EPMC6322687 | biostudies-literature

Iridium-catalyzed direct asymmetric reductive amination utilizing primary alkyl amines as the N-sources.

Project description:Direct asymmetric reductive amination is one of the most efficient methods for the construction of chiral amines, in which the scope of the applicable amine coupling partners remains a significant challenge. In this study we describe primary alkyl amines effectively serve as the N-sources in direct asymmetric reductive amination catalyzed by the iridium precursor and sterically tunable chiral phosphoramidite ligands. The density functional theory studies of the reaction mechanism imply the alkyl amine substrates serve as a ligand of iridium strengthened by a (N)H-O(P) hydrogen-bonding attraction, and the hydride addition occurs via an outer-sphere transition state, in which the Cl-H H-bonding plays an important role. Through this concise procedure, cinacalcet, tecalcet, fendiline and many other related chiral amines have been synthesized in one single step with high yields and excellent enantioselectivity.

| S-EPMC9187633 | biostudies-literature

Direct Amination of α-Hydroxy Amides.

Project description:A TiCl4-mediated reaction for the direct amination of α-hydroxy amides has been developed. This simple, general, additive/base/ligand-free reaction is mediated by economical TiCl4. The reaction runs under mild conditions. This highly efficient C-N bond formation protocol is valid for diverse amines, including primary, secondary and heterocyclic amines, and even a primary amide and indole.

| S-EPMC7451067 | biostudies-literature

Direct amination of ?-halo-?-ketoesters with anilines.

Project description:The direct amination of ?-haloacetoacetates with anilines is described. Compared to existing methods, this simple protocol provides an attractive strategy to prepare diverse ?-anilino-?-ketoesters in one step. Good to excellent yields of the amination products were obtained under robust conditions, providing versatile and useful scaffolds.

| S-EPMC3321089 | biostudies-literature

Effects of ruthenium hydride species on primary amine synthesis by direct amination of alcohols over a heterogeneous Ru catalyst.

Project description:Heterogeneously catalysed synthesis of primary amines by direct amination of alcohols with ammonia has long been an elusive goal. In contrast to reported Ru-based catalytic systems, we report that Ru-MgO/TiO2 acts as an effective heterogeneous catalyst for the direct amination of a variety of alcohols to primary amines at low temperatures of ca. 100 °C without the introduction of H2 gas. The present system could be applied to a variety of alcohols and provides an efficient synthetic route for 2,5-bis(aminomethyl)furan (BAMF), an attention-getting biomonomer. The high catalytic performance can be rationalized by the reactivity tuning of Ru-H species using MgO. Spectroscopic measurements suggest that MgO enhances the reactivity of hydride species by electron donation from MgO to Ru.

| S-EPMC8162067 | biostudies-literature

Direct Amination of Cobaltocenium Hexafluoridophosphate via Vicarious Nucleophilic Substitution.

Project description:In this communication we report a convenient, as short as possible synthesis of aminocobaltocenium hexafluoridophosphate, a very useful compound for further functionalization in cobaltocenium chemistry. Via vicarious nucleophilic substitution of hydrogen of cobaltocenium hexafluoridophosphate with 1,1,1-trimethylhydrazinium iodide as nucleophile bearing its own leaving group, a one-step amination of cobaltocenium in 50% isolated yield is possible, a major improvement over the standard multistep procedure involving common Curtius rearrangement chemistry.

| S-EPMC6550438 | biostudies-literature

Direct stereospecific amination of alkyl and aryl pinacol boronates.

Project description:The direct amination of alkyl and aryl pinacol boronates is accomplished with lithiated methoxyamine. This reaction directly provides aliphatic and aromatic amines, stereospecifically, and without preactivation of the boronate substrate.

| S-EPMC3481838 | biostudies-literature

Direct amination of homoenolates catalyzed by N-heterocyclic carbenes.

Project description:N-Heterocyclic carbenes derived from N-mesityl-N-methyltriazolium salts are effective catalysts for generating homoenolate species from alpha,beta-unsaturated aldehydes. The unique intermediate adds to the electrophilic nitrogen of 1-acyl-2-aryldiazenes, and the resulting activated carbonyl unit undergoes an intramolecular acylation event. This formal [3+2] cycloaddition between alpha,beta-unsaturated aldehydes and acylaryldiazenes, catalyzed by an N-heterocyclic carbene, produces substituted pyrazolidinones in good yields. This new NHC-catalyzed reaction accommodates aromatic and alkyl alpha,beta-unsaturated aldehydes and various aromatic diazenes. A chiral triazolium salt catalyzes the formation of the pyrazolidinone product in moderate yield and good enantioselectivity. The pyrazolidinones can undergo reductive N-N bond cleavage to give beta-amino acid derivatives.

| S-EPMC2981089 | 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