Three-component Coupling Reaction Research Articles

Synthesis of Benzoxaphosphole 1-Oxide Heterocycles via a Three-Component Coupling Reaction Involving Arynes, Phosphites, and Ketones.

An efficient and transition-metal-free three-component reaction with benzynes formed in situ from 2-(trimethylsilyl)aryl triflate, phosphites, and ketones was developed for the synthesis of benzoxaphosphole 1-oxides. An array of benzoxaphosphole 1-oxides were prepared from both activated and non-activated ketones in moderate to good yields with a broad functional group tolerance. This reaction is useful for preparing organophosphorus compounds encountered in natural products and materials.

Highly Efficient Single A3-Coupling (Aldehyde-Amine-Alkyne) Reaction Catalyzed by Air Stable Silver-(N-Heterocyclic Carbene) Complexes: Synthesis and Characterization

The interaction of N,N-disubstituted benzimidazolium salts 2a–e with Ag2O formed new silver-(N-heterocyclic carbene) complexes 3a–e. Structural characterization of silver-(N-heterocyclic carbene) complexes was conducted by using NMR, FT-IR and elemental analysis. Preliminary catalytic studies using all the silver complexes 3a–e were performed on three-component coupling reaction of a series of aldehydes with alkynes and amines was demonstrated. Most of these reactions led to formation of the expected propargylamines in good conversions using low amounts catalyst and obviating both the use of purified reagents as employ of a glovebox. Complexes 3a and 3c exhibited good catalytic activities under neat conditions. The silver complexes 3a–e showed luminescence properties in CH3CN at room temperature.

Pd-Catalyzed three-component decarboxylative coupling reactions between alkylidene pyrazolones, allyl carbonates and active methylene compounds.

Under the catalysis of Pd2(dba)3·CHCl3/(±)-L5 in THF at room temperature, the three-component decarboxylative coupling reactions among alkylidene pyrazolones, allyl carbonates and active methylene compounds proceeded readily and furnished the desired products in acceptable chemical yields. The chemical architecture of the obtained products was unambiguously confirmed by single crystal X-ray analysis.

Electrosynthesis of S-thiocarbamates with disulfides as a sulfur source.

An electrochemical oxidative synthesis of S-thiocarbamates by a carbamothioation reaction via a three-component coupling reaction (disulfide, water and isocyanide) is developed, which avoids the use of external oxidants and generates only hydrogen gas as the by-product. With NH4I as the mediator and electrolyte, the desired S-thiocarbamates were obtained in good yields in an undivided cell at room temperature.

Electricity-driven three-component reductive coupling reaction for the synthesis of diarylmethylamine.

A three-component reductive coupling reaction of aldehydes, amines and cyanopyridines under electrochemical conditions has been developed. The in situ generated imine and cyanopyridine simultaneously undergo single-electron reduction at the cathode, and afford diarylmethylamines through radical coupling without the participation of reducing agents. The one-pot electrolysis method can modularly obtain various secondary and tertiary amines and exhibits broad functional group compatibility. Mechanistic experiments verify the pivotal reduction step from imine to α-amino radical and reveal the key role of benzoic acid in reducing the reduction potential of imine and cyanopyridine.

Copper-catalyzed three-component N-alkylation of quinazolinones and azoles.

A Cu-catalyzed three-component N-alkylation coupling reaction of N-heteroarenes with methyl ketones and DMPA as a carbon source has been developed. Using methyl ketones as alkylation reagents and DMPA (N,N'-dimethylpropionamide) as a carbon source, the reaction proceeded smoothly under the Cu-based oxidative system and led to a series of functionalized N-heterocycles including 4-quinazolinones, triazoles and pyrazoles.

Transition-metal-catalyzed one-pot selenylation of electrophilic arylating agents using triphenyltin chloride/Se as a phenylselenating agent.

Three novel and efficient protocols for the synthesis of phenyl aryl selenides through a three-component coupling reaction of triphenyltin chloride with aryl halides, phenolic esters or nitroarenes, and Se powder catalyzed by CuI or Cu(OAc)2 in the presence of a base in PEG200 at 90-100 °C have been developed. Also, NiFe2O4 as a magnetically reusable nanocatalyst was applied in these reactions under similar reaction conditions. The present methods are superior to other currently available methods due to the use of triphenyltin chloride/Se as a phenylselenating agent and phenolic esters and nitroarenes as a coupling partner for C-Se-C bond formation for the first time, a green solvent and inexpensive and reusable catalysts, and avoidance of any toxic and expensive arylselenating reagents.

Transition-metal-free three-component coupling approach to QUINAP derivatives.

The aluminum(III) triflate catalyzed three-component coupling reaction of alkynes, amines and phosphorylated aryl aldehydes to access phosphoryl quinoline derivatives has been developed. The reaction proceeds in a simple system without the use of transition metals, ligands or additives, thus making it attractive for the fast preparation of a variety of new potential N-P bidentate ligands.

Ni-Catalyzed Three-Component Coupling Reaction of Butadiene,Aldimines and Alkenylboronic Acids

Ni-Catalyzed Three-Component Coupling Reaction of Butadiene,Aldimines and Alkenylboronic Acids

From A3/KA2 to AYA/KYA multicomponent coupling reactions with terminal ynamides as alkyne surrogates – a direct, green route to γ-amino-ynamides

A copper-catalysed three-component coupling reaction between a carbonyl derivative, a terminal ynamide and an amine has been developed for the one-pot construction of γ-amino-ynamides under mild and environmentally-friendly conditions.

Palladium/Copper-Cocatalyzed Arylsilylation of Internal Alkynes with Acyl Fluorides and Silylboranes: Synthesis of Tetrasubstituted Alkenylsilanes by Three-Component Coupling Reaction.

In this Letter, the palladium/copper-cocatalyzed arylsilylation of internal alkynes with acyl fluorides and silylboranes is described. This is the first example in which acyl fluorides have been utilized for the three-component coupling reaction via decarbonylation, yielding a variety of tetrasubstituted alkenylsilanes in moderate to good yields.

A New Saddle-Shaped Aza Analog of Tetraphenylene: Atroposelective Synthesis and Application as a Chiral Acylating Reagent

A New Saddle-Shaped Aza Analog of Tetraphenylene: Atroposelective Synthesis and Application as a Chiral Acylating Reagent

Clean Synthesis of Propargylamines Using Novel Magnetically Recyclable Silver Nanocatalyst (AgMNPs)

A novel and green magnetic nanocatalyst were synthesized by anchoring silver (I) to (2-iminomethyl)pyridine moiety. The prepared nanocatalyst was identified by different techniques, such as FT-IR, XRD, SEM, EDX, VSM, and TGA analyses. The nanocatalyst exhibited significant catalytic activity and recoverability in a three-component coupling reaction of aldehyde, amine, and terminal alkyne to produce a variety of propargylmines. This impactful method furnished the desired products under mild reaction conditions, in excellent yield (91–98%) and lower reaction time (25–45 min). The nanocatalyst was easily recovered by an external magnet and reused in10 consecutive cycles without a considerable decrease in its activity and selectivity.

A Unified Approach for the Synthesis of Isourea and Isothiourea from Isonitrile and N,N-Dibromoarylsulfonamides.

A unified approach has been developed for the synthesis of both isourea and isothiourea in a three-component coupling reaction by treating alcohols or thiols respectively with N,N-dibromoarylsulfonamides and isonitrile and in the presence of K2CO3. This metal-free process proceeds via carbodiimide intermediate at room temperature within a very short reaction time. A library of sulfonylisoureas and isothioureas has been made using this synthetic protocol with wide substrate scope in good to high yields.

Pd/GF-Phos-Catalyzed Asymmetric Three-Component Coupling Reaction to Access Chiral Diarylmethyl Alkynes.

Significant attention has been given in the past few years to the selective transformations of N-tosylhydrazones to various useful compounds. However, the development of enantioselective versions poses considerable challenges. Herein we report a Pd-catalyzed enantioselective three-component coupling of N-tosylhydrazone, aryl halide, and terminal alkyne under mild conditions utilizing a novel chiral sulfinamide phosphine ligand (GF-Phos), which provides a facile access to chiral diarylmethyl alkynes, which are useful synthons in organic synthesis as well as exist as the skeleton in many bioactive molecules. A pair of enantiomers of the product could be easily prepared using the same chiral ligand by simply changing the aryl substituents of the N-tosylhydrazone and aryl halide. The salient features of this reaction include the readily available starting materials, general substrate scope, high enantioselectivity, ease of scale-up, mild reaction conditions, and versatile transformations.

SYNTHESIS, CHARACTERIZATION AND CYCLAZATION OF PYRAN USING Ag2O NANOPARTICLE FROM NATURAL SOURCE “GINGER”

This study was aimed to synthesis Ag2O nanoparticles (N.P.s) utilizing the Ginger plant (Zingiber officinale) extract. As catalysts for pyran derivatives formation employing a three-component coupling reaction among aromatic and aliphatic aldehydes, malononitrile, and dimedone. The nanoparticles exhibit robust catalytic activity with high productivity. Results revealed that Ag2O NPs improved various vital features, like higher yields, reaction time, simple chemical separation, catalytic economic efficiency, and quick process. This study aimed to cyclize heterocyclic compounds to provide new hetero compounds applying nano-oxides obtained from natural (unmanufactured) sources and used in several medical, pharmaceutical, and industrial implementations. The outcomes nanoparticles were examined by Fourier Transform Infrared spectroscopy (FTIR) and transmission electron microscopy (T.E.M.); the chemical characteristics of the outcome compounds were tested by spectroscopy techniques (FTIR spectroscopy and 1H-NMR).

Photoinduced Copper Catalysis in an Asymmetric Three-Component Coupling Reaction

Key words copper photoredox catalysis - 1,3-dienes - three-component reaction

Stereoselective Synthesis of Dihydrocoumarins via [1,2]-Phospha-Brook Rearrangement in Three-Component Coupling Reaction of α-Ketoesters, o-Quinone Methides, and Dialkyl Phosphites.

A highly regio- and diastereoselective approach for the synthesis of phosphate substituted dihydrocoumarins via Brønsted base catalyzed [1,2]-phospha-Brook rearrangement is reported. The two-step, one-pot Michael addition of α-phosphonyloxy enolates proceeds by coupling of dialkyl phosphite and α-ketoesters to o-quinone methides, followed by an intramolecular cyclization, providing 3,4-dihydrocoumarin frameworks.

Synthesis of N-protected 1-aminoalkylphosphonium salts—a new perspective

The current study presents two novel and efficient strategies for the synthesis of N-protected 1-aminoalkylphosphonium salts from readily available substrates. The first one is a one-pot methodology which is based on the three-component coupling reaction of aldehydes with amides, carbamates, lactams, imides, or urea in the presence of triarylphosphonium salt. This approach results in the production of a wide range of structurally diverse N-protected 1-aminoalkylphosphonium salts. The second one is a step-by-step procedure which results in the synthesis of N-protected 1-aminomethylphosphonium salts only, and hence has a limited scope of application. This method is performed in two steps: transformation of amide-type substrates to the corresponding hydroxymethyl derivatives and substitution of the hydroxyl group with triarylphosphine. Both protocols are promising alternatives and complement the hitherto described methodologies.

Regio- and Stereoselective Synthesis of Multi-Alkylated Allylic Boronates through Three-Component Coupling Reactions between Allenes, Alkyl Halides, and a Diboron Reagent.

Multisubstituted allylic boronates are attractive and valuable precursors for the rapid and stereoselective construction of densely substituted carbon skeletons. Herein, we report the first synthetic approach for differentially 2,3,3-trialkyl-substituted allylic boronates that contain a stereodefined tetrasubstituted alkene structure. Copper(I)-catalyzed regio- and stereoselective three-component coupling reactions between gem-dialkylallenes, alkyl halides, and a diboron reagent afforded sterically congested allylic boronates. The allylboration of aldehydes diastereoselectively furnished the corresponding homoallylic alcohols that bear a quaternary carbon. A computational study revealed that the selectivity-determining mechanism was correlated to the coordination of a boryl copper(I) species to the allene substrate as well as the borylcupration step.