Browse
Submit Data
Databases
API
Help

Dataset Information

46 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Electrochemical Dehydrogenative C(sp² )-H Amination.

ABSTRACT: A transition-metal-free direct electrolytic C-H amination involving an electrochemically generated nitrenium ion intermediate has been developed. The electrosynthesis takes place in the absence of any organoiodine catalysts and is enabled by an in situ generated electrolyte. A novel, efficient intramolecular and intermolecular C-H amination has been demonstrated using a simple reaction setup.

SUBMITTER: Puthanveedu M

PROVIDER: S-EPMC8251997 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Electrochemical Dehydrogenative C(sp2 )-H Amination.

Puthanveedu Mahesh M Khamraev Vladislav V Brieger Lukas L Strohmann Carsten C Antonchick Andrey P AP

Chemistry (Weinheim an der Bergstrasse, Germany) 20210501 30

A transition-metal-free direct electrolytic C-H amination involving an electrochemically generated nitrenium ion intermediate has been developed. The electrosynthesis takes place in the absence of any organoiodine catalysts and is enabled by an in situ generated electrolyte. A novel, efficient intramolecular and intermolecular C-H amination has been demonstrated using a simple reaction setup. ...[more]

PMID: 33931904

Similar Datasets

Copper-catalyzed dehydrogenative γ-C(sp3)-H amination of saturated ketones for synthesis of polysubstituted anilines.

Project description:Metal-catalyzed β-C-H functionalization of saturated carbonyls via dehydrogenative desaturation proved to be a powerful tool for simplifying synthesis of valuable β-substituted carbonyls. Here, we report a copper-catalyzed dehydrogenative γ-C(sp3)-H amination of saturated ketones that initiates the three-component coupling of saturated ketones, amines and N-substituted maleimides to construct polysubstituted anilines. The protocol presented herein enables both linear and α-branched butanones to couple a wide spectrum of amines and various N-substituted maleimides to produce diverse tetra- or penta-substituted anilines in fair-to-excellent yields with good functional group tolerance. The mechanism studies support that this ketone dehydrogenative γ-C(sp3)-H amination was triggered by the ketone α,β-dehydrogenation desaturation that activates the adjacent γ-C(sp3)-H bond towards functionalization. This α,β-dehydrogenation desaturation-triggered cascade sequence opens up a new avenue to the remote C(sp3)-H functionalization of saturated ketones and has the potential to enable the rapid syntheses of complex compounds from simple starting materials.

| S-EPMC6695438 | biostudies-literature

Merging Photochemistry with Electrochemistry: Functional-Group Tolerant Electrochemical Amination of C(sp3 )-H Bonds.

Project description:Direct amination of C(sp3 )-H bonds is of broad interest in the realm of C-H functionalization because of the prevalence of nitrogen heterocycles and amines in pharmaceuticals and natural products. Reported here is a combined electrochemical/photochemical method for dehydrogenative C(sp3 )-H/N-H coupling that exhibits good reactivity with both sp2 and sp3 N-H bonds. The results show how use of iodide as an electrochemical mediator, in combination with light-induced cleavage of intermediate N-I bonds, enables the electrochemical process to proceed at low electrode potentials. This approach significantly improves the functional-group compatibility of electrochemical C-H amination, for example, tolerating electron-rich aromatic groups that undergo deleterious side reactions in the presence of high electrode potentials.

| S-EPMC6482061 | biostudies-literature

Cobalt-catalysed site-selective intra- and intermolecular dehydrogenative amination of unactivated sp(3) carbons.

Project description:Cobalt-catalysed sp(2) C-H bond functionalization has attracted considerable attention in recent years because of the low cost of cobalt complexes and interesting modes of action in the process. In comparison, much less efforts have been devoted to the sp(3) carbons. Here we report the cobalt-catalysed site-selective dehydrogenative cyclization of aliphatic amides via a C-H bond functionalization process on unactivated sp(3) carbons with the assistance of a bidentate directing group. This method provides a straightforward synthesis of monocyclic and spiro β- or γ-lactams with good to excellent stereoselectivity and functional group tolerance. In addition, a new procedure has been developed to selectively remove the directing group, which enables the synthesis of free β- or γ-lactam compounds. Furthermore, the first cobalt-catalysed intermolecular dehydrogenative amination of unactivated sp(3) carbons is also realized.

| S-EPMC4366490 | biostudies-literature

Copper-Mediated Dehydrogenative C(sp3)-H Borylation of Alkanes.

Project description:Borylations of inert carbon-hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis of these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated borylations involving hydrogen atom transfer pathways have emerged as attractive alternatives because they provide complimentary regioselectivities and proceed under metal-free conditions. However, these net oxidative processes require stoichiometric oxidants and therefore cannot compete with the high atom economy of their precious-metal-catalyzed counterparts. Herein, we report that CuCl2 catalyzes radical-mediated, dehydrogenative C(sp3)-H borylations of alkanes with bis(catecholato)diboron under oxidant-free conditions. This is a result of an unexpected dual role of the copper catalyst, which promotes oxidation of the diboron reagent to generate an electrophilic bis-boryloxide that acts as an effective borylating agent in subsequent redox-neutral photocatalytic C-H borylations.

| S-EPMC10360158 | biostudies-literature

Copper(ii) ketimides in sp3 C-H amination.

Project description:Commercially available benzophenone imine (HN[double bond, length as m-dash]CPh2) reacts with β-diketiminato copper(ii) tert-butoxide complexes [CuII]-O t Bu to form isolable copper(ii) ketimides [CuII]-N[double bond, length as m-dash]CPh2. Structural characterization of the three coordinate copper(ii) ketimide [Me3NN]Cu-N[double bond, length as m-dash]CPh2 reveals a short Cu-Nketimide distance (1.700(2) Å) with a nearly linear Cu-N-C linkage (178.9(2)°). Copper(ii) ketimides [CuII]-N[double bond, length as m-dash]CPh2 readily capture alkyl radicals R˙ (PhCH(˙)Me and Cy˙) to form the corresponding R-N[double bond, length as m-dash]CPh2 products in a process that competes with N-N coupling of copper(ii) ketimides [CuII]-N[double bond, length as m-dash]CPh2 to form the azine Ph2C[double bond, length as m-dash]N-N[double bond, length as m-dash]CPh2. Copper(ii) ketimides [CuII]-N[double bond, length as m-dash]CAr2 serve as intermediates in catalytic sp3 C-H amination of substrates R-H with ketimines HN[double bond, length as m-dash]CAr2 and t BuOO t Bu as oxidant to form N-alkyl ketimines R-N[double bond, length as m-dash]CAr2. This protocol enables the use of unactivated sp3 C-H bonds to give R-N[double bond, length as m-dash]CAr2 products easily converted to primary amines R-NH2 via simple acidic deprotection.

| S-EPMC8654034 | biostudies-literature

Electrochemical C(sp3)-H Fluorination.

Project description:A simple and robust method for electrochemical alkyl C-H fluorination is presented. Using a simple nitrate additive, a widely available fluorine source (Selectfluor), and carbon-based electrodes, a wide variety of activated and unactivated C-H bonds were converted to their C-F congeners. The scalability of the reaction was also demonstrated with a 100 gram preparation of fluorovaline.

| S-EPMC7990259 | biostudies-literature

γ-Selective C(sp3)-H amination via controlled migratory hydroamination.

Project description:Remote functionalization of alkenes via chain walking has generally been limited to C(sp3)-H bonds α and β to polar-functional units, while γ-C(sp3)-H functionalization through controlled alkene transposition is a longstanding challenge. Herein, we describe NiH-catalyzed migratory formal hydroamination of alkenyl amides achieved via chelation-assisted control, whereby various amino groups are installed at the γ-position of aliphatic chains. By tuning olefin isomerization and migratory hydroamination through ligand and directing group optimization, γ-selective amination can be achieved via stabilization of a 6-membered nickellacycle by an 8-aminoquinoline directing group and subsequent interception by an aminating reagent. A range of amines can be installed at the γ-C(sp3)-H bond of unactivated alkenes with varying alkyl chain lengths, enabling late-stage access to value-added γ-aminated products. Moreover, by employing picolinamide-coupled alkene substrates, this approach is further extended to δ-selective amination. The chain-walking mechanism and pathway selectivity are investigated by experimental and computational methods.

| S-EPMC8476554 | biostudies-literature

Electrochemical Benzylic C(sp3)-H Acyloxylation.

Project description:The development of sustainable C(sp3)-H functionalization methods is of great interest to the pharmaceutical and agrochemical industries. Anodic oxidation is an efficient means of producing benzylic cations that can undergo subsequent in situ nucleophilic attack to afford functionalized benzylic products. Herein, we demonstrate the suitability of carboxylic acids as nucleophiles to yield benzylic esters. This method employs a series of secondary benzylic substrates and functionalized carboxylic acids and is demonstrated on a gram scale in flow.

| S-EPMC9315976 | biostudies-literature

Electrochemical [4 + 1] Tandem sp3(C-H) Double Amination for the Direct Synthesis of 3-Acyl-Functionalized Imidazo[1,5-a]pyridines.

Project description:3-Acyl imidazo[1,5-a]pyridines, featured pharmaceutical moieties that were prepared by a three-step reaction conventionally, could be obtained in one step by an electrochemical tandem sp3 (C-H) double amination of acetophenones with pyridine ethylamines using ammonium iodide as a redox mediator.

| S-EPMC8829863 | biostudies-literature

Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization.

Project description:Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

| S-EPMC6217814 | biostudies-literature