An efficient synthesis of propargylamines via three-component coupling of aldehydes, amines and alkynes catalyzed by nanocrystalline copper(II) oxide

An efficient three-component coupling of aldehydes, amines and alkynes to prepare propargylamines, in nearly quantitative yields using nanocrystalline CuO as a catalyst is described. Structurally divergent aldehydes and amines were converted to the corresponding propargylamines. The reaction does not require any co-catalyst. After completion of the reaction, the catalyst was recovered by centrifugation and reused several times with only a slight decrease of activity observed under the same reaction conditions.     

Diastereoselective synthesis of pyrrolidines via the Yb(OTf)3 catalyzed three-component reaction of aldehydes, amines, and 1,1-cyclopropanediesters

[Chemical reaction: see text] Aldimines, generated in situ by the reaction of primary amines or anilines with aldehydes, undergo smooth reaction with various 1,1-cyclopropanediesters in the presence of catalytic Yb(OTf)3. The products are pyrrolidines in which the major diastereomer bears a cis relationship between substituents at the 2- and 5-positions. In most cases the diastereoselectivity is greater than 10:1.     

An efficient and facile one-pot synthesis of propargylamines by three-component coupling of aldehydes, amines, and alkynes via C-H activation catalyzed by NiCl2

NiCl₂ was found to be a highly efficient and effective catalyst for the one-pot three-component (A³) coupling of aldehydes, amines, and alkynes to produce propargylamines in nearly quantitative yields. Structurally divergent aldehydes, amines, and alkynes were converted into the corresponding propargylamines. No co-catalyst or activator is needed and water is the only byproduct of this novel protocol.     

The rhodium catalyzed three-component reaction of diazoacetates, titanium(IV) alkoxides and aldehydes

The rhodium(II)-catalyzed three-component reaction of diazoacetates, titanium alkoxides and aldehydes is shown to give alpha-alkoxyl-beta-hydroxyl acid derivatives; the novel C-C bond formation reaction is proposed to occur through oxonium ylides derived from diazo compounds and titanium alkoxides, and followed by intermolecular trapping by aldehydes.     

Gold(III) (C^N) complex-catalyzed synthesis of propargylamines via a three-component coupling reaction of aldehydes, amines and alkynes

Propargylamines are synthesized in high yields via a gold(III) (C^N) complex-catalyzed three-component coupling reaction of aldehydes, amines and alkynes in water at 40 °C. Excellent diastereoselectivities (up to 99:1) have been achieved when chiral prolinol derivatives are employed as the amine component. Notably, the [Au(C^N)Cl₂] complex (N^CH = 2-phenylpyridine) could be repeatedly used for 10 reaction cycles, leading to an overall turnover number of 812.     

A three-component synthesis of homoallylic amines catalyzed by CuI

Cuprous iodide is a very effective catalyst for the three-component condensation of an aldehyde, benzylamine and allyltributylstannane in DMF to produce homoallylic amines in high yields.     

Rhodium(III) iodide hydrate catalyzed three-component coupling reaction: synthesis of α-aminonitriles from aldehydes, amines, and trimethylsilyl cyanide

Aryl imines formed from aldehydes and amines undergo smoothly in situ nucleophilic addition with trimethylsilyl cyanide (TMSCN) in the presence of catalytic amount of hydrated rhodium(III) iodide to afford the corresponding α-aminonitriles in excellent yield. The low catalytic loading (2 mol %), mild experimental conditions, and short reaction time (mostly within 13 min) represent the key features of this novel catalytic system.     

CuCl catalyzed green and efficient one-pot synthesis of aminoindolizine frameworks via three-component reactions of aldehydes, secondary amines, and terminal alkynes in PEG

CuCl catalyzes efficient synthesis of aminoindolizine scaffolds by one-pot reactions in PEG of pyridine- or quinoline-2-carboxaldehydes with secondary amines and terminal alkynes via tandem C-H activation, coupling, and cyclization reactions. The reactions are easy to perform, atom-economic, environment friendly, broad in scope, and allow the generation of a number of biologically potent aminoindolizine frameworks from readily accessible starting materials.     

Selective synthesis of secondary amines by Pt nanowire catalyzed reductive amination of aldehydes and ketones with ammonia

The process of the reductive amination of aldehydes or ketones in the presence of ammonia using unsupported ultra-thin Pt nanowires has been developed. This catalytic system shows high activity and selectivity under mild reaction conditions.     

Direct synthesis of Cbz-protected β-amino ketones by iodine-catalyzed three-component condensation of aldehydes, ketones and benzyl carbamate

Iodine has been found to be very effective catalyst for a Mannich reaction between an aryl aldehyde, an aryl ketone and benzyl carbamate, even though this is a less reactive amine, to produce Cbz-protected β-aryl β-amino carbonyl compounds in high yields.     

Molecular iodine-catalyzed and air-mediated tandem synthesis of quinolines via three-component reaction of amines, aldehydes, and alkynes

A one-pot synthesis of quinolines via molecular iodine-catalyzed and air-mediated tandem condensation/imino-Diels-Alder/isomerization/oxidation of simple readily available amines, aldehydes, and alkynes has been developed. This methodology was extended to synthesize quinazolines from two molecules of amines and two molecules of glyoxalates.     

Highly efficient trialkylsilylcyanation of aldehydes, ketones and imines catalyzed by a nucleophilic N-heterocyclic carbene

The synthetic utility of N-heterocyclic carbenes was demonstrated by the trialkylsilylcyanation of aldehydes, ketones and imines. In the presence of a catalytic amount of 3a, the reactions with Me₃SiCN proceeded smoothly to give the corresponding cyanohydrin trimethylsilyl ethers or amino nitrile derivatives in good to excellent yields.     

Gold-catalyzed three-component annulation: efficient synthesis of highly functionalized dihydropyrazoles from alkynes, hydrazines, and aldehydes or ketones

Polysubstituted dihydropyrazoles were directly obtained by a gold-catalyzed three-component annulation. This reaction consists of a Mannich-type coupling of alkynes with N,N'-disubstituted hydrazines and aldehydes/ketones followed by intramolecular hydroamination. Cascade cyclization using 1,2-dialkynylbenzene derivatives as the alkyne component was also performed producing fused tricyclic dihydropyrazoles in good yields.     

One-pot, three-component synthesis of secondary amines and trisubstituted hydrazines from ketones

Various imines and hydrazones were reduced to the corresponding amines and hydrazines using borane-tetrahydrofuran complex as a reducing agent in the solution of lithium perchlorate in diethyl ether. The initial imines or hydrazones have been prepared at the same conditions just before the reduction step. Both steps were carried out in one vessel with a good yield and insignificant formation of by-products.     

Diastereoselective aldol reaction of N,N-dibenzyl-alpha-amino aldehydes with ketones catalyzed by proline

[reaction: see text] L-proline-catalyzed direct aldol reaction of L-amino acid-derived N,N-dibenzyl amino aldehydes with acetone, cyclopentanone, or hydroxyacetone provides gamma-amino-beta-hydroxy- or gamma-amino-alpha,beta-dihydroxy-ketones with moderate to excellent yields and diastereoselectivities.     

Sequential catalytic process: synthesis of quinoline derivatives by AuCl3/CuBr-catalyzed three-component reaction of aldehydes, amines, and alkynes

A sequential catalytic process has been developed based on gold-catalyzed nucleophilic addition of terminal alkynes to imines, and gold-catalyzed intramolecular reaction of aromatic ring to alkynes. This one-pot reaction of aldehydes, amines, and alkynes gives quinoline derivatives in good yields.     

An efficient synthesis of polyhydroacridine derivatives by the three‐component reaction of aldehydes,amines and dimedone in ionic liquid

In this paper the preparation of 3,3,6,6‐tetramethyl‐9,10‐diaryl‐1,2,3,4,5,6,7,8,9,10‐decahydroacridine‐1,8‐dione derivatives from aldehydes, aromatic amines and 5,5‐dimethyl‐1,3‐cyclohexanedione in 1‐n‐butyl‐3‐methylimidazolium bromide ([bmim]Br) is described. The structures of these compounds were characterized by elemental analysis, IR and ¹H NMR spectra and further confirmed by single crystal X‐ray diffraction analysis.     

Rh(I)-catalyzed three-component reaction of 2,3-allenoates, organoboronic acids, and aldehydes. An efficient synthesis of α,β-unsaturated δ-lactones

α,β-Unsaturated δ-lactones were efficiently prepared by an Rh(I)-catalyzed three-component reaction of 2,3-allenoates, organoboronic acids, and aldehydes. The reaction may proceed via a sequential transmetalation, carbometalation of 2,3-allenoates, insertion of aldehydes, and lactonization process.     

l-Proline catalyzed efficient and convenient synthesis of substituted 2H-chromenes by three-component reaction

A convenient and efficient method is described for the synthesis of alkoxy substituted 2H-chromens by l-proline catalyzed reaction of salicylaldehydes with diketone in alcohol. The method is applicable for various substituted salicylaldehydes and aliphatic as well as benzylic alcohols.     

Chiral phosphoric acid-catalyzed enantioselective three-component Mannich reaction of acyclic ketones,aldehydes and anilines

1. Download high-res image (111KB)
2. Download full-size image