Metal-complex ionosilicas: Cationic mesoporus silica with Ni(II) and Cu(II) complexes in their framework

Metal-complex ionosilicas with cationic complexes into the mesoporous silica framework were prepared using anionic surfactants. The electrostatic interaction between the anionic surfactant and the cationic metal complexes incorporated in the silica framework allows for the fine tuning of the mesoporous structure. The gentle procedure of synthesis developed and mild ion-exchange extraction of the surfactant, allowed a cleaner route for the immobilization of homogeneous cationic catalysts in mesoporous silica, while protecting the structural and chemical integrity of the metal complexes.

Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes

Chiral complexes formed by privileged phosphoramidites derived from chiral binol and optically pure Davies’ amines, and copper(II) triflate, silver(I) triflate or silver(I) benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between nitroalkenes and azomethine ylides generated from α-amino acid derived imino esters. These three methods can be conducted at room temperature to afford the exo-cycloadducts (4,5-trans-2,5-cis-4-nitroprolinates) with high diastereoselectivity and high enantioselectivity. In general, the three procedures are complementary but silver catalysts are more versatile and less sensitive to sterically congested starting materials.

Palladium(II) complexes with a phosphino-oxime ligand: synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes

The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CH[double bond, length as m-dash]NOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CH[double bond, length as m-dash]NOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.

Palladium(II) pincer complexes of α-amino acids: towards the synthesis of catalytically active artificial peptides

NCN palladium(II) complexes have been covalently attached to the N- and C-terminus of the dipeptide L-Phe-L-Va-OMe. Remarkably, the hydrolysis of the NCN-Pd(II) L-Val-OMe afforded the corresponding, palladated free amino acid without affecting the metal site. This deprotected amino acid could be coupled to any protein, enzyme or peptidic chain by simple peptide chemistry. This bioorganometallic systems were active as catalysts in the aldol reaction between methyl isocianate and benzaldehyde.

New hybrid materials based on the grafting of Pd(II)-amino complexes on the graphitic surface of AC: preparation, structures and catalytic properties

A novel procedure for the preparation of solid Pd(II)-based catalysts consisting of the anchorage of designed Pd(II)-complexes on an activated carbon (AC) surface is reported. Two molecules of the Ar–S–F type (where Ar is a plane-pyrimidine moiety, F a Pd(II)-ligand and S an aliphatic linker) differing in F, were grafted on AC by π–π stacking of the Ar moiety and the graphene planes of the AC, thus favouring the retaining of the metal-complexing ability of F. Adsorption of Pd(II) by the AC/Ar–S–F hybrids occurs via Pd(II)-complexation by F. After deep characterization, the catalytic activities of the AC/Ar–S–F/Pd(II) hybrids on the hydrogenation of 1-octene in methanol as a catalytic test were evaluated. 100% conversion to n-octane at T = 323.1 K and P = 15 bar, was obtained with both catalysts and most of Pd(II) was reduced to Pd(0) nanoparticles, which remained on the AC surface. Reusing the catalysts in three additional cycles reveals that the catalyst bearing the F ligand with a larger Pd-complexing ability showed no loss of activity (100% conversion to n-octane) which is assigned to its larger structural stability. The catalyst with the weaker F ligand underwent a progressive loss of activity (from 100% to 79% in four cycles), due to the constant aggregation of the Pd(0) nanoparticles. Milder conditions, T = 303.1 K and P = 1.5 bar, prevent the aggregation of the Pd(0) nanoparticles in this catalyst allowing the retention of the high catalytic efficiency (100% conversion) in four reaction cycles.

Efficient Diastereo- and Enantioselective Synthesis of exo-Nitroprolinates by 1,3-Dipolar Cycloadditions Catalyzed by Chiral Phosphoramidite⋅Silver(I) Complexes

Chiral complexes formed by privileged phosphoramidites and silver triflate or silver benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between azomethine ylides generated from α-amino acid-derived imino esters and nitroalkenes affording with high dr the exo-cycloadducts 4,5-trans-2,5-cis-4-nitroprolinates in high ee at room temperature. In general, better results are obtained using silver rather than copper(II) complexes. In many cases the exo-cycloadducts can be obtained in enantiomerically pure form just after simple recrystallization. The mechanism and the justification of the experimentally observed stereodiscrimination of the process are supported by DFT calculations. These enantiomerically enriched exo-nitroprolinates can be used as reagents for the synthesis of nitropiperidines, by ester reduction and ring expansion, which are inhibitors of farnesyltransferase.