A novel atom-economic synthesis of functionalized imidazolidines through copper(I)-catalyzed domino three-component coupling and cyclization reactions

An interesting approach to functionalized imidazolidines is described. These compounds are obtained in a copper(I)-catalyzed domino three-component coupling and cyclization reaction involving two formaldehyde-derived imine units and a terminal alkyne. Alternatively, imidazolidines can be obtained from propargylamines and formaldehyde-derived imines. This strategy provides a straightforward and atom-economic pathway to construct imidazolidines with high yields and benefits from readily available starting materials, convenient one-pot operations.     

A microwave-assisted click chemistry synthesis of 1,4-disubstituted 1,2,3-triazoles via a copper(I)-catalyzed three-component reaction

A microwave-assisted three-component reaction was used to prepare a series of 1,4-disubstituted-1,2,3-triazoles from corresponding alkyl halides, sodium azide, and alkynes. This procedure eliminates the need to handle organic azides, as they are generated in situ, making this already powerful click process even more user-friendly and safe.     

Organocatalysed three-component domino synthesis of 1,4-dihydropyridines under solvent free conditions

An organocatalysed protocol for one-pot synthesis of 1,4-dihydropyridines via three-component coupling of cinnamaldehyde, aniline and β-keto esters under solvent free conditions at ambient temperature is reported. The reaction is generally very fast and the products are obtained in high yield. The catalytic activity of small organic molecules like amino acids (acidic, basic and neutral), ephedrine and cinchona alkaloids was studied.     

A new three-component domino synthesis of 1,4-dihydropyridines

Cerium ammonium nitrate (CAN) catalyzed the three-component domino reaction between aromatic amines, α,β-unsaturated aldehydes, and ethyl acetoacetate, providing an efficient new entry into 1,4-dihydropyridines. This new reaction requires very mild reaction conditions, has water as the only side product and is complementary to the classical Hantzsch synthesis in that it is well suited to the preparation of N-aryl-5,6-unsubstituted dihydropyridines. Experiments in the presence of a radical trap suggest that a one-electron oxidative mechanism can be excluded and that CAN acts as a Lewis acid.     

An efficient synthesis of embelin derivatives through domino Knoevenagel hetero Diels-Alder reactions under microwave irradiation

The synthesis of novel pyrano embelin derivatives has been achieved through domino Knoevenagel hetero Diels-Alder reactions of embelin (1) with paraformaldehyde and electron rich alkenes. This synthetic approach is highly efficient when microwave irradiation is used.     

Rh(I)-catalyzed solvent-free ortho-alkylation of aromatic imines under microwave irradiation

The synthesis of ortho-alkylated ketones through a chelation-assisted Rh (I) catalyzed ortho-alkylation reaction of aromatic imines under microwave activated solvent-free conditions in monomode reactors was performed. These conditions have been also applied to hydroacylation and ortho-alkylation reactions with aldimines.     

An efficient three-component domino synthesis of difluoromethyl-containing 1,4-dihydropyridines under solvent and catalyst free conditions

The difluoromethyl-containing Hantzsch 1,4-dihydropyridines were synthesized in good yields by a one-pot cyclocondensation of ethyl difluoroacetoacetate (EDFAA), a variety of aromatic aldehydes and ammonium acetate under solvent and catalyst free conditions. The comparison of reaction conditions and products was made among the different 1,3-carbonyl substrates (ethyl acetoacetate, ethyl difluoroacetoacetate and ethyl trifluoroacetoacetate) for the Hantzsch reaction.     

CuI-catalyzed domino reactions for the synthesis of benzoxazine-fused isoquinolines under microwave irradiation

A small library of benzoxazine-fused isoquinolines has been synthesized under microwave irradiation (MW) via CuI-catalyzed domino reactions of o-alkynyl aldehydes and amines having embedded nucleophiles. This strategy offers a operationally simple, environmentally acceptable route to synthesize benzoxazine-fused isoquinolines in moderate to good yields. All new compounds were characterized by ¹H NMR, ¹³C NMR, infrared, and high-resolution mass spectrometry techniques.     

One-pot copper(I)-catalyzed synthesis of 3,5-disubstituted isoxazoles

[reaction: see text] 3,5-Disubstituted isoxazoles are obtained in good yields by a convenient one-pot, three-step procedure utilizing a regioselective copper(I)-catalyzed cycloaddition reaction between in situ generated nitrile oxides and terminal acetylenes. Most functional groups do not interfere with the reaction, which can be performed in aqueous solvents without protection from oxygen. Since all reagents are used in stoichiometric amounts, formation of byproducts is minimized.     

One pot synthesis of indene through copper(I)-catalyzed three-components coupling and cyclization reaction

A new and efficient synthesis of substituted indene has been achieved via copper(I)-catalyzed domino three-component coupling and cyclization reaction in moderate to good yield.     

Enantioselective,copper(I)-catalyzed three-component reaction for the synthesis of β,γ-alkynyl α-amino acid derivatives

The first catalytic asymmetric three-component reaction of ethyl glyoxylate, para-anisidine, and aliphatic, aromatic alkynes catalyzed by CuOTf·0.5C₆H₆/pybox 7 has been developed. The protocol provided the corresponding chiral β,γ-alkynyl α-amino acid derivatives in good yields and 66–74% ee.     

Practical one-pot synthesis of 5-alkynyl-1,2,3-triazoles via heterogeneous copper(I)-catalyzed tandem three-component click/alkynylation reaction

An efficient and practical route to 5-alkynyl-1,2,3-triazoles has been developed via heterogeneous tandem CuAAC/alkynylation reaction of organic azides, alkynes and 1-bromoalkynes by using an L-proline-functionalized MCM-41-anchored copper(I) complex [L-Proline-MCM-41-CuCl] as catalyst under mild conditions. The reaction produces a wide variety of 5-alkynyl-1,2,3-triazoles in mostly good to excellent yields. The new immobilized copper(I) complex can be readily prepared from commercially available and inexpensive reagents and displays the same catalytic activity as CuCl. The L-Proline-MCM-41-CuCl catalyst is also easy to recover via a simple filtration process and can be reused at least seven times without apparent loss of activity.     

Iron(III)-catalyzed three-component domino strategy for the synthesis of imidazo[1,2-a]pyridines

An efficient, one-pot, three-component domino strategy has been demonstrated for the synthesis of imidazo[1,2-a]pyridines using a catalytic amount of Fe(III) chloride in high yields in air. A library of imidazo[1,2-a]pyridines was synthesized by the reaction of easily available aldehydes and 2-aminopyridines in a mixture of nitroalkane and DMF (2:1). This transformation presumably occurs by a sequential aza-Henry reaction/cyclization/denitration. The use of readily available chemicals as starting materials, inexpensive metal catalyst, aerobic reaction conditions, tolerance of a wide range of functional groups, and operational simplicity are the notable advantages of this present protocol.     

Sc(OTf)3-catalyzed, solvent-free domino synthesis of functionalized pyrazoles under controlled microwave irradiation

An efficient, rapid, and green synthesis of functionalized pyrazoles has been accomplished under solvent-free conditions by the reaction of phenyl hydrazine, aldehydes and ethyl acetoacetate. This approach exploits the synthetic potential of microwave irradiation and scandium triflate combination and offers many advantages such as excellent product yields, shorter reaction time, easy isolation of products, and environmentally benign reaction conditions.     

An efficient and solvent-free one-pot synthesis of 1,4-dihydropyridines under microwave irradiation

An efficient synthesis of 1,4-dihydropyridines using lanthanum oxide as a catalyst from aldehydes,β-ketoester and ammonium acetate without solvent under the irradiation of microwave is described.Compared with the classical Hantzsch reaction,this new method has the advantage of good yield(90-98%) and short reaction time(40-80 s).     

Cu(I)-catalyzed domino reactions: efficient and selective synthesis of 4H-chromenes and naphthalenes

Depending on the ratio of the substrates and the reaction conditions, the Cu(I)-catalyzed domino reaction between bromobenzyl bromides and β-ketoesters exclusively yields either 4H-chromenes or naphthalenes.     

Asymmetric synthesis of dihydropyranones from ynones by sequential copper(I)-catalyzed direct aldol and silver(I)-catalyzed oxy-Michael reactions

Ynones as diene surrogates: the asymmetric synthesis of enantiomerically enriched substituted dihydropyranones is described. The products are obtained in two steps by a copper(I)-catalyzed direct aldol reaction of ynones followed by a silver-catalyzed oxy-Michael reaction. This easy method is compatible with both aromatic and aliphatic substrates, and provides excellent chemoselectivity under mild reaction conditions.     

Manganese(III) acetate-mediated synthesis of biaryls under microwave irradiation

Manganese(III) acetate (Mn(OAc)₃)-mediated synthesis of biaryls and heterobiaryls starting from arylboronic acid was developed under microwave irradiation in high yields. Microwaves were also used for the synthesis of Mn(OAc)₃ from KMnO₄ and acetic acid. Additional irradiation of this in situ generated Mn(OAc)₃ with arylboronic acids, which in turn furnished the biaryls in high yields in a one pot reaction. This is superior from the point of view of yield, short reaction time, sensitive functional group toleration, and more environmentally friendly than the reported methods with a minimum amount of benzene and thiophene as a reagent but not as a solvent.