One-pot Three-component Mannich-type Reactions Research Articles

Fe3O4@saponin/Cd: a novel magnetic nano-catalyst for the synthesis of β-aminoketone derivatives

A novel recyclable magnetic core–shell nanoparticles Fe3O4@saponin/Cd was synthesized by the combination of nano-Fe3O4@saponin with cadmium acetate. The structure, magnetic features, and morphology of magnetic nanoparticles (MNPs) Fe3O4@saponin/Cd were studied totally via different experiments, such as Fourier transform infrared (FT-IR) spectroscopy, energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), inductively coupled plasma (ICP), high-resolution transmission electron microscopy (HR-TEM), and Brunauer–Emmett–Teller (BET). It was found that the catalyst was active for the synthesis of β-aminoketone derivatives via one-pot three-component Mannich-type reactions of ketones, aromatic aldehydes, aromatic amines under eco-friendly solvent, at room temperature. Furthermore, this catalyst can be easily recovered magnetically and can be reused for other runs without any reduction in the activity.

Deep eutectic solvent immobilized on SBA-15 as a novel separable catalyst for one-pot three-component Mannich reaction

An environmentally friendly and recyclable nanocomposite (HNMPCl/ZnCl2/SBA-15) was prepared by impregnation of N-methylpyrrolidonium-zinc chloride based deep eutectic solvent (HNMPCl/ZnCl2) on SBA-15. The catalytic activity of HNMPCl/ZnCl2/SBA-15 was investigated towards the one-pot three-component Mannich type reaction to a series of aldehydes, ketones, and amines and provided excellent activity and selectivity for the synthesis of β-amino ketones under mild reaction condition in green solvent. The HNMPCl/ZnCl2/SBA-15 was prepared using simple method from readily available starting material and was confirmed by FTIR, SEM, XRD, BET, and EDX. This protocol features green and efficient catalyst, ease of work up, simple separation without chromatography and reusability of the HNMPCl/ZnCl2/SBA-15 for four runs are the important highlights of this process, that it will find a wide variety of applications in academic and industrial research.

An environmentally friendly, photocontrollable and highly recyclable catalyst for use in a one-pot three-component Mannich reaction

An environmentally friendly, photocontrollable and highly recyclable catalyst (ZrOPPAZOSO3H) has been synthesized by the immobilization of 4-[4-(6-phosphonic acid-hexanoxyl)phenylazo]benzenesulfonic acid onto zirconium phosphonate. This catalyst was characterized by Fourier transform infrared, scanning electron microscopy, X-ray powder diffraction, nitrogen adsorption-desorption and UV–vis analyses. The catalytic activity of ZrOPPAZOSO3H was investigated towards the one-pot three-component Mannich-type reaction of benzaldehyde, aniline and cyclohexanone in water at room temperature, and gave excellent yields. Interestingly, the catalytic activity could be regulated by photoirradiation. Furthermore, upon completion of the reaction, the product could be readily separated by extraction, and the water phase reused in the next run. Lastly, the catalyst could be readily recovered by centrifugation and reused up to six times without any discernible impact on its activity.

ChemInform Abstract: SnTUD‐1: A Solid Acid Catalyst for Three Component Coupling Reactions at Room Temperature.

A novel wormhole structured mesoporous material containing tin, SnTUD-1, was prepared by a direct hydrothermal synthesis method using triethanolamine (TEA) as an organic inexpensive mesoporous structure directing agent. XRD and N2 sorption studies of SnTUD-1 confirmed the amorphous mesoporous nature of SnTUD-1, which possessed a large surface area of 555 m2 g−1 and a pore diameter of 7.4 nm. HR-TEM further ascertained the disordered pores in their morphology and the presence of nano-domains of SnO2 species. The nature of the Sn4+ ion co-ordination with the silica matrix was evaluated by using different techniques including diffuse reflectance UV-Vis, FTIR, 29Si MAS NMR and XPS. SnTUD-1 had an interesting Lewis acidity as measured by FTIR of pyridine adsorption which provided excellent activities in one-pot three-component Mannich-type reactions of ketones with aldehydes and amines at room temperature.

SnTUD-1: a solid acid catalyst for three component coupling reactions at room temperature

A novel wormhole structured mesoporous material containing tin, SnTUD-1, was prepared by a direct hydrothermal synthesis method using triethanolamine (TEA) as an organic inexpensive mesoporous structure directing agent. XRD and N2 sorption studies of SnTUD-1 confirmed the amorphous mesoporous nature of SnTUD-1, which possessed a large surface area of 555 m2 g−1 and a pore diameter of 7.4 nm. HR-TEM further ascertained the disordered pores in their morphology and the presence of nano-domains of SnO2 species. The nature of the Sn4+ ion co-ordination with the silica matrix was evaluated by using different techniques including diffuse reflectance UV-Vis, FTIR, 29Si MAS NMR and XPS. SnTUD-1 had an interesting Lewis acidity as measured by FTIR of pyridine adsorption which provided excellent activities in one-pot three-component Mannich-type reactions of ketones with aldehydes and amines at room temperature.

An efficient synthesis of β-amino ketone compounds through one-pot three-component Mannich-type reactions using bismuth nitrate as catalyst

Three components one-pot Mannich reaction of aromatic ketone, aromatic aldehyde and aromatic amines has been efficiently catalyzed by recyclable bismuth nitrate (Bi(NO3)3, BN) at ambient temperature to give various β-amino carbonyl compounds in high yields. This method has advantages of mild condition, no environmental pollution, and simple work-up procedures. Most importantly, β-amino carbonyl compounds with ortho-substituted aromatic amines are obtained in acceptable to moderate yields by this methodology.

(±)-Camphor-10-sulfonic acid catalyzed direct one-pot three-component Mannich type reaction of alkyl (hetero)aryl ketones under solvent-free conditions: application to the synthesis of aminochromans

Direct three-component Mannich type reactions of (hetero)aromatic ketones with aromatic aldehydes and aromatic amines were efficiently catalyzed by camphor-10-sulfonic acid at ambient temperature under solvent free conditions to afford β-amino ketones in good to excellent yields. Syntheses of aminochromans were accomplished from one of the Mannich adducts via an unprecedented route involving intramolecular etherification with CuI/8-hydroxyquinoline.

ChemInform Abstract: H3PW12O40 Supported on Silica‐Encapsulated γ‐Fe2O3 Nanoparticles: A Novel Magnetically‐Recoverable Catalyst for Three‐Component Mannich‐Type Reactions in Water.

AbstractThe separation of the catalyst is achieved by magnetism.

Highly Efficient Synthesis of β-Amino Ketones via Direct Mannich-type Reaction Catalyzed by Acidic Ionic Liquid

An ionic liquid-catalyzed one-pot three-component Mannich-type reaction of aromatic aldehydes, aromatic amines and cyclohexanone is presented.

One-pot three-component Mannich-type reaction catalyzed by trifluoromethanesulfonic acid in water

One-pot three-component Mannich-type reaction of ketones, aldehydes and amines was efficiently catalyzed by liquid trifluoromethanesulfonic acid in water at ambient temperature. The high yield of corresponding β-amino ketones compounds were achieved. The proposed method is mild, green, simple and efficient.

H3PW12O40 supported on silica-encapsulated γ-Fe2O3 nanoparticles: a novel magnetically-recoverable catalyst for three-component Mannich-type reactions in water

A new type of magnetically-recoverable catalyst was synthesized by the immobilization of H3PW12O40 on the surface of silica-encapsulated γ-Fe2O3 nanoparticles. This catalyst was characterized by transmission electron microscopy (TEM), a laser particle size analyzer, infrared spectroscopy (IR) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The results show that the particles are mostly spherical in shape and have an average size of approximately 94 nm. The characterization data derived from IR spectroscopy reveal that H3PW12O40 on the support exists in the Keggin structure. The acidity of the catalyst was measured by a potentiometric titration with n-butylamine. To our surprise, this very strong solid acid catalyst showed an excellent distribution of acid sites, suggesting that the catalyst possesses a higher number of surface active sites compared to its homogeneous analogues. The activity of the catalyst was probed through one-pot three-component Mannich-type reactions of aldehydes, amines and ketones in water at room temperature. The excellent conversions show that the catalyst has strong and sufficient acidic sites, which are responsible for its catalytic performance. After the reaction, the catalyst/product separation could be easily achieved with an external magnetic field, and more than 95% of the catalyst could usually be recovered. The catalyst was reused at least five times without any loss of its high catalytic activity.

One-pot three-component Mannich-type reactions using Sulfamic acid catalyst under ultrasound irradiation

Sulfamic acid (NH 2SO 3H, SA) was used as an efficient, inexpensive, non-toxic and recyclable green catalyst for the ultrasound-assisted one-pot Mannich reaction of aldehydes with ketones and amines. This ultrasound protocol has advantages of high yield, mild condition, no environmental pollution, and simple work-up procedures. Most importantly, β-aminocarbonyl compounds with ortho-substituted aromatic amines are obtained in acceptable to good yields by this methodology for the first time.

Functionalized ionic liquid as the recyclable catalyst for Mannich-type reaction in aqueous media

Abstract A novel functionalized ionic liquid 3-(N,N-dimethyldodecylammonium)propanesulfonic acid hydrogen sulfate ([DDPA][HSO4]) was prepared. The ionic liquid could be used as a Bronsted acid–surfactant-combined catalyst for one-pot three-component Mannich-type reaction at room temperature in water. The heterogeneous catalytic procedure was simple and the catalyst could be reused at least six times without noticeably decreasing the catalytic activity.

Silica-supported aluminum chloride: A recyclable and reusable catalyst for one-pot three-component Mannich-type reactions

Silica-supported aluminum chloride was used as an efficient, recyclable and reusable catalyst for the one-pot Mannich-type reactions of acetophenone with aromatic aldehydes and aromatic amines. This protocol has advantages of high yield, mild condition, no environmental pollution, and simple work-up procedure.

Design and Synthesis of a Water-Tolerant Chiral Indium Complex: ­Application to One-Pot Three-Component Mannich-Type Reactions in Water

A novel chiral indium(III) camphorsulfonate complex prepared from indium trichloride, allyltributylstannane and (1S)-(+)-10-camphorsulfonic acid has been developed as a water-tolerant Lewis acid to afford high yields (up to 99%) in one-pot three-component Mannich-type reactions in a true water environment.