Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-free approach for imidazole synthesis via one-pot N-α-C(sp3)-H bond functionalization of benzylamines.

ABSTRACT: A metal-free one-pot method is established for the synthesis of tetrasubstituted imidazoles from the reaction of arylmethylamines and 1,2-dicarbonyls/benzoin. The N-α-C(sp3)-H bond functionalization of arylmethylamines using a catalytic amount of AcOH afforded polysubstituted imidazoles under aerobic conditions in significant yields of up to 95%.

SUBMITTER: Kadu VD

PROVIDER: S-EPMC11375450 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Metal-free approach for imidazole synthesis via one-pot N-α-C(sp3)-H bond functionalization of benzylamines.

Kadu Vikas D VD Thokal Machhindra S MS Godase Rajkumar K RK Kotali Bhagyashree C BC Wadkar Pooja S PS

RSC advances 20240905 39

A metal-free one-pot method is established for the synthesis of tetrasubstituted imidazoles from the reaction of arylmethylamines and 1,2-dicarbonyls/benzoin. The N-α-C(sp3)-H bond functionalization of arylmethylamines using a catalytic amount of AcOH afforded polysubstituted imidazoles under aerobic conditions in significant yields of up to 95%. ...[more]

PMID: 39239291

Similar Datasets

Practical, metal-free remote heteroarylation of amides via unactivated C(sp3)-H bond functionalization.

Project description:Development of practical methods for the production of multi-functionalized amides is one of the most important topics in both synthetic chemistry and drug discovery. Disclosed herein is a new, efficient, site-selective heteroarylation of amides via C(sp3)-H bond functionalization. Amidyl radicals are directly generated from the amide N-H bonds under mild conditions, which trigger the subsequent 1,5-HAT process. A wide scope of aliphatic amides including carboxamides, sulfonamides, and phosphoramides are readily modified at remote C(sp3)-H bonds by installing diverse heteroaryl groups. Borne out of pragmatic consideration, this protocol can be used for the late-stage functionalization of amides.

| S-EPMC6640195 | biostudies-literature

Metal-free C(sp3)-H functionalization of sulfonamides via strain-release rearrangement.

Project description:With the increasing awareness of sustainable chemistry principles, the development of an efficient and mild strategy for C(sp3)-H bond activation of nitrogen-containing compounds without the utilization of any oxidant and metal is still highly desired and challenging. Herein, we present a metal-free reaction system that enables C-H bond functionalization of aliphatic sulfonamides using DABCO as a promoter under mild conditions, affording a series of α,β-unsaturated imines in good yields with high selectivities. This protocol tolerates a broad range of functionalities and can serve as a powerful synthetic tool for the late-stage modification of complex compounds. More importantly, control experiments and detailed DFT calculations suggest that this process involves [2 + 2] cyclization/ring-cleavage reorganization, which opens up a new platform for the establishment of other related reorganization reactions.

| S-EPMC8179522 | biostudies-literature

Acid-Catalyzed, Metal- and Oxidant-Free C=C Bond Cleavage of Enaminones: One-Pot Synthesis of 3,4-Dihydroquinazolines.

Project description:In this study, we present the HOAc-catalyzed selective cleavage of the C=C double bond of enaminones, enabling the formation of a new C-N bond and a new C=N bond for the one-pot synthesis of 2-substituted 3,4-dihydroquinazolines directly from ynones and 2-(aminomethyl)anilines. This method operates in ethanol under transition-metal-free and oxidant-free conditions, offering a sustainable and efficient approach for the synthesis of 3,4-dihydroquinazolines with broad functional group tolerance.

| S-EPMC11767836 | biostudies-literature

Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization.

Project description:The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both a N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated.

| S-EPMC3233640 | biostudies-literature

1-Aminopyridinium Ylides as Monodentate Directing Groups for sp3 C-H Bond Functionalization.

Project description:1-Aminopyridinium ylides are efficient directing groups for palladium-catalyzed β-arylation and alkylation of sp3 C-H bonds in carboxylic acid derivatives. The efficiency of these directing groups depends on the substitution at the pyridine moiety. The unsubstituted pyridine-derived ylides allow functionalization of primary C-H bonds, while methylene groups are unreactive in the absence of external ligands. 4-Pyrrolidinopyridine-containing ylides are capable of C-H functionalization in acyclic methylene groups in the absence of external ligands, thus rivaling the efficiency of the aminoquinoline directing group. Preliminary mechanistic studies have been performed. A cyclopalladated intermediate has been isolated and characterized by X-ray crystallography, and its reactivity was studied.

| S-EPMC6880753 | biostudies-literature

Iodine-mediated C-N and N-N bond formation: a facile one-pot synthetic approach to 1,2,3-triazoles under metal-free and azide-free conditions.

Project description:A novel strategy towards the synthesis of 1,4-disubstituted 1,2,3-triazoles via C-N and N-N bond formation has been demonstrated under transition metal-free and azide-free conditions. These 1,2,3-triazoles were obtained in a regioselective manner from commercially available anilines, aryl alkenes/aryl alkynes and N-tosylhydrazines using I2 under O2 atmosphere. Broad substrate scope, milder reaction conditions, good to moderate yields and clean protocol are the notable features of the method. Moreover, this protocol is amenable for the generation of a library of medicinally important key building blocks.

| S-EPMC9070426 | biostudies-literature

Metal-free visible-light-promoted C(sp3)-H functionalization of aliphatic cyclic ethers using trace O2.

Project description:Presented is a light-promoted C-C bond forming reaction yielding sulfone and phosphate derivatives at room temperature in the absence of metals or photoredox catalyst. This transformation proceeds in neat conditions through an auto-oxidation mechanism which is maintained through the leaching of trace amounts of O2 as sole green oxidant.

| S-EPMC10181853 | biostudies-literature

Intramolecular C(sp3 )-H Bond Oxygenation by Transition-Metal Acylnitrenoids.

Project description:This study demonstrates for the first time that easily accessible transition-metal acylnitrenoids can be used for controlled direct C(sp3 )-H oxygenations. Specifically, a ruthenium catalyst activates N-benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C-H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2-diols. The method can be applied to the chemoselective C-H oxygenation of benzylic, allylic, and propargylic C(sp3 )-H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst-controlled fashion between C-H oxygenation and C-H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp3 )-H into C(sp3 )-O bonds.

| S-EPMC7756817 | biostudies-literature

One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides.

Project description:A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a SRN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.

| S-EPMC5572204 | biostudies-literature

C-H Functionalization of Imidazo[1,5-a]pyridines: A Metal-Free Approach for Methylene Insertion to Access C(sp2)-C(sp3)-H-C(sp2) Bond Formation.

Project description:Formaldehyde has been used as a solvent and a source of carbon to insert a methylene group for bridging two imidazo[1,5-a]pyridine molecules without using any metal catalysis. This strategy has been extended on other alkyl-, aryl-, and heteroaryl aldehydes as well. This C(sp2)-C(sp3)-H-C(sp2) bond forming reaction proceeds via C(sp2)H functionalization of imidazo[1,5-a]pyridine and was applied on a wide range of substrates offering moderate to good yields of methylene-bridged/inserted bis-imidazo[1,5-a]pyridines. Most importantly, as an application, the bis-heteroarene product has been demonstrated as a ligand. The ligand-like behavior of bis-imidazo[1,5-a]pyridines has been demonstrated as an extension of current methodology. This reaction works well at the gram scale level.

| S-EPMC11656365 | biostudies-literature