Synthesis Of Propargylamines Research Articles

Ultrasonic and bio‐assisted synthesis of Ag@HNTs‐T as a novel heterogeneous catalyst for the green synthesis of propargylamines: A combination of experimental and computational study

A novel heterogeneous catalyst is prepared through functionalization of halloysite nanotube with 1H‐1,2,3‐triazole‐5‐methanol and subsequent immobilization of silver nanoparticles through bio‐assisted approach using Arctiumplatylepis extract. The resulting catalyst, Ag@HNTs‐T, was characterized by using SEM/EDX, BET, XRD, FTIR, ICP‐AES, TGA, DTGA and elemental mapping analysis. Moreover, we computationally assessed metal‐ligand interactions in Ag@HNTs‐T complex model to interpret the immobilization behavior of silver nanoparticles on HNTs surface via quantum chemistry computations. The catalytic activity of the catalyst was studied for the synthesis of propargylamines via A3 and KA2 coupling reactions under ultrasonic irradiation. The results demonstrated that Ag@HNTs‐T could efficiently promote these reactions to furnish the corresponding products in high yields and short reaction times. The study of the recyclability of the catalyst and Ag(0) leaching confirmed that the catalyst was recyclability up to four reaction runs with slight Ag(0) leaching.

Cu2O nanoparticles supported hydrothermal carbon microspheres as catalyst for propargylamine synthesis

Cu2O nanoparticles supported on hydrothermal carbon microsphere (HTC) have been synthesized by hydrothermal synthesis followed by chemical reduction method. The prepared catalyst was used for propargylamine synthesis from the coupling of phenyl acetylene with benzaldehyde and piperidine. In this protocol, biomass derived D-glucose was used as carbon source for the synthesis of carbon microspheres by hydrothermal treatment and CuCl2·6H2O as a copper precursor. The activity of Cu2O@HTC was compared with different catalysts such as CuFe2O4, CuCl2·2H2O, commercial CuO, and Cu2O. Among them Cu2O@HTC exhibited the best activity and selectivity for propargylamine synthesis. The catalyst was well characterized by several analytical techniques such as SEM, XRD, FTIR, TEM, ICP-AES, and XPS analysis before and after 5th reuse. The effect of various parameters was studied including solvent, catalyst loading, mole ratio and temperature of the reaction to achieve the best yield at 60 °C and 1.5 × 10−3 g/cm3 catalyst loading. Notably, Cu2O@HTC was recycled five times and found to be robust.

Cover Image

The cover image, by Samahe Sadjadi et al., is based on the Full Paper Green bio-based synthesis of Fe2O3@SiO2-IL/Ag hollow spheres and their catalytic utility for ultrasonic-assisted synthesis of propargylamines and benzo[b]furans. DOI: 10.1002/aoc.4029.

A 12-Fold ThSi2 Interpenetrated Network Utilizing a Glycine-Based Pseudopeptidic Ligand

We report the synthesis and characterization of a 3D Cu(II) coordination polymer, [Cu3(L1)2(H2O)8]·8H2O (1), with the use of a glycine-based tripodal pseudopeptidic ligand (H3L1 = N,N′,N″-tris(carboxymethyl)-1,3,5-benzenetricarboxamide or trimesoyl-tris-glycine). This compound presents the first example of a 12-fold interpenetrated ThSi2 (ths) net. We attempt to justify the unique topology of 1 through a systematic comparison of the synthetic parameters in all reported structures with H3L1 and similar tripodal pseudopeptidic ligands. We additionally explore the catalytic potential of 1 in the A3 coupling reaction for the synthesis of propargylamines. The compound acts as a very good heterogeneous catalyst with yields up to 99% and loadings as low as 3 mol %.

Efficient Method for the Synthesis of Propargylamines Using a Biomaterial Containing Copper Nanoparticles as Impressive and Reusable Nanocatalyst

Preparation and catalytic performance of nanosized copper particles supported on expanded corn starch (ECS) was investigated. The catalyst was characterized by inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray powder diffraction (XRD), N2-sorption analysis, thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). The copper nanoparticles supported on expanded corn starch (CuNPs@ECS) were found to be a very efficient and durable catalyst for the preparation of propargylamines by three component reaction of secondary amines, aldehydes and alkynes. The catalyst can be successfully recycled and reused without significant loss of efficiency in 4 reaction runs. The procedure described here offers an easy and practical method accompanied by higher yields, and environmentally benign system. Keywords: Aldehyde, amine, copper, expanded-starch, nanosized, propargylamine.

Carbon Nitride‐Supported Silver Nanoparticles: Microwave‐ Assisted Synthesis of Propargylamine and Oxidative C‐C Coupling Reaction

AbstractIn the present study we have, synthesized silver nanoparticles supported on carbon nitride AgNPs@g‐C3N4 and investigated its catalytic aspects by using microwave. We found that silver nanoparticles supported on g‐C3N4 were highly active in the A3‐coupling reaction of (Aldehyde, secondary amine and terminal alkynes) for the synthesis of propargylamines with excellent yield up to 97% and in C−C coupling reaction of terminal alkynes for the synthesis of 1, 3‐diyne with excellent yield up to 98%. We have achieved excellent TON (72932), TOF (3636 min−1), E‐factor (0.27) and atom economy AE (94%). Reaction parameters like effect of catalyst quantity, effect of time and effect of temperature was deeply studied. The catalyst was characterized by SEM, HR‐TEM, EDX, XRD, ICP‐AES and IR.

Progress in Synthesis of Propargylamine and Its Derivatives by Nanoparticle Catalysis via A3 coupling: A Decade Update

AbstractPropargylamine and its derivatives are important skeletal structure for synthesis of many nitrogen containing active biological and pharmaceutical compounds. They are classically prepared from aldehyde, amine and alkyne (A3 coupling) which proved to be an exciting method since water is the only by‐product with the desired compound. Three component coupling strategies are very attractive research domain in organic chemistry during the past two decades for the synthesis of highly functionalized organic molecules. Molecular diversity in three component reactions ends up with several methods for drug discovery process towards the synthesis of structurally tailored heterocyclic compounds. These one pot transformation processes do involve simultaneous addition of reactants, reagents and catalyst. The reactions are generally carried out by employing several transition metal catalysts. Nanoparticles have shown their potential as catalysts in several fields of chemical research in modern era. Now, they have taken entry in multicomponent reaction system for playing the role of a catalyst. This review highlights a library of metal nanoparticles which have been used in recent years for synthesis of propargylamine and its derivatives via A3 coupling reactions.

Zinc(II)‐Catalyzed Synthesis of Propargylamines by Coupling Aldimines and Ketimines with Alkynes

A ZnII‐catalyzed reaction between imines, which were derived from unactivated aldehydes or ketones and primary amines or α‐amino acid esters, and terminal alkynes has led to the rapid and efficient formation of tri‐ and tetrasubstituted propargylamines (from aldimines and ketimines, respectively) in good to excellent yields. No additives or extra Lewis acid reagents were required for the imine‐alkyne coupling reaction.

Tunable Prussian blue analogues for the selective synthesis of propargylamines through A3 coupling

M1[Co(CN)6]2/3-type Prussian blue analogues (M1–Co PBAs) were studied as catalysts for the synthesis of propargylamines via A3 coupling of phenylacetylene, benzaldehyde and piperidine.

One-pot synthesis of azacyclodiynes by reaction of α,ω-diacetylenes with 1,5,3-dioxazepanes using copper-containing catalysts

An effective method has been developed for the synthesis of cyclic propargylamines by aminomethylation of α,ω-diacetylenes with N-alkyl-substituted 1,5,3-dioxazepanes in the presence of copper-containing catalysts.

Synthesis and crystal structures of salen-type Cu(ii) and Ni(ii) Schiff base complexes: application in [3+2]-cycloaddition and A3-coupling reactions

The synthesis and characterisation of two new salen-type Schiff base complexes of the type [Cu(L)]·0.5H2O and [Ni(L)], and their application in the synthesis of 5-substituted 1H-tetrazoles and propargylamines are described.

Microwave assisted one pot three component synthesis of propargylamine, tetra substituted propargylamine and pyrrolo[1,2-a]quinolines using CuNPs@ZnO–PTh as a heterogeneous catalyst

A Cu@ZnO–PTh nanocomposite was synthesized and used as a heterogeneous catalyst for KA2 and A3 coupling, which is a highly efficient and green technique.

Recyclable Cu/C3N4 composite catalyzed AHA/A3 coupling reactions for the synthesis of propargylamines.

The heterogeneous Cu/C3N4 catalyst was found to be efficient for the synthesis of propargylamines using a three-component coupling reaction of alkynes, CH2Cl2 and amines (AHA) without additional base. Moreover, the catalyst also showed highly catalytic activity in the synthesis of C1-alkynylated tetrahydroisoquinolines (THIQs) via an A3 reaction of alkynes, aldehydes and THIQ. The Cu/C3N4-catalyzed multicomponent reactions exhibited good functional group tolerance in most examples. Furthermore, the easily prepared Cu/C3N4 catalyst could be recovered and reused conveniently over 5 times without losing catalytic activities.

Metal- and catalyst-free, one-pot, three-component synthesis of propargylamines in magnetized water: experimental aspects and molecular dynamics simulation

Multi-component reactions of aldehydes, amines, and alkynes in magnetized water as a green-promoting medium.

Synthesis of propargylamines catalyzed by nano-colloidal silica-tethered polyhedral oligomeric silsesquioxanes with eight branches of 3-aminopropyltriethoxysilane as an efficient catalyst

AbstractHere, we report a family of polyhedral oligomeric silsesquioxanes with eight branches of 3-aminopropyltriethoxysilane tethered to nano-colloidal silica, which is characterized by

Synthesis and Reactivity of Propargylamines in Organic Chemistry.

Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A3 couplings and C-H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

Stabilization of Au NPs on symmetrical tridentate NNN-Pincer ligand grafted on magnetic support as water dispersible and recyclable catalyst for coupling reaction of terminal alkyne

A symmetrical tridentate NNN-pincer ligand derived from 2-aminopyridine/cyanuric chloride was covalently grafted onto the surface of modified magnetic support to stabilize Au nanoparticles. Spectroscopic evidence (IR, XRD, EDX, TEM, and XRF) and other analyses (TGA, VSM, and H2-TPR) confirmed successful immobilization and desired catalyst structure. Catalyst loading of 0.07–0.1 mol% was shown to be very effective in the synthesis of propargylamines through addition of terminal alkynes to amine/aldehyde adduct (A3-coupling). The water-dispersible catalyst allows the use of water as an inexpensive solvent. The high accessibility and robustness of the catalyst enhanced reusability so that no deactivation of catalyst or aggregation of supported Au NPs is observed after seven repeated recycling. Control experiments also showed the true heterogeneous nature of the catalyst in the reaction without significant leaching. All experiments showed that the catalyst is comparable to or even more active than the corresponding species in solution.

Asymmetric synthesis of propargylamines as amino acid surrogates in peptidomimetics.

The amide moiety of peptides can be replaced for example by a triazole moiety, which is considered to be bioisosteric. Therefore, the carbonyl moiety of an amino acid has to be replaced by an alkyne in order to provide a precursor of such peptidomimetics. As most amino acids have a chiral center at Cα, such amide bond surrogates need a chiral moiety. Here the asymmetric synthesis of a set of 24 N-sulfinyl propargylamines is presented. The condensation of various aldehydes with Ellman’s chiral sulfinamide provides chiral N-sulfinylimines, which were reacted with (trimethylsilyl)ethynyllithium to afford diastereomerically pure N-sulfinyl propargylamines. Diverse functional groups present in the propargylic position resemble the side chain present at the Cα of amino acids. Whereas propargylamines with (cyclo)alkyl substituents can be prepared in a direct manner, residues with polar functional groups require suitable protective groups. The presence of particular functional groups in the side chain in some cases leads to remarkable side reactions of the alkyne moiety. Thus, electron-withdrawing substituents in the Cα-position facilitate a base induced rearrangement to α,β-unsaturated imines, while azide-substituted propargylamines form triazoles under surprisingly mild conditions. A panel of propargylamines bearing fluoro or chloro substituents, polar functional groups, or basic and acidic functional groups is accessible for the use as precursors of peptidomimetics.

Copper–birhodanine complex immobilized on Fe3O4 nanoparticles: DFT studies and heterogeneous catalytic applications in the synthesis of propargylamines in aqueous medium

Heterogeneous magnetic nanocatalyst, Fe3O4@SiO2–Ligand–Cu (II) MNPs, reveals high catalytic performance within the synthesis of propargylamines using the multicomponent coupling reaction of aldehydes, phenylacetylene and secondary amines in water as a solvent. The substantial feature of this organic–inorganic hybrid magnetic nanocatalyst is the capability of straightforward separation of the reaction mixture by an external magnet which was retrieved ten times without significant loss of catalytic activity. This methodology has other advantages such as subordination to the principles of green chemistry and avoiding the use of expensive and harmful organic solvents. To study the stability and actual structure of birhodanine derivative–copper (II) complex, DFT calculations were also performed.

Formation of α-Monosubstituted Propargylamines from Terminal Alkynes and Secondary Amines Using a (PNO)Rh/Cu Tandem Catalyst System

A novel (PNO)Rh/CuBr (PNO: phosphine-quinolinolate) tandem catalyst system was developed for facile synthesis of α-monosubstituted propargylamines from aliphatic terminal alkynes and secondary amines. Various terminal alkynes and amines were applicable to this reaction and the corresponding propargylamines were obtained in good yields.