Alessandro Caselli

• Professor
• Università degli Studi di Milano at University of Milan

Despite extensive research into developing efficient and environmentally friendly catalysts for converting CO2 over the last decade, the search for a robust and cost‐effective catalytic system is ongoing. This study describes developing and applying a new catalytic system using inexpensive ferrate and zincate anions immobilized on easily available...

2,5‐disubstituted N,N’‐alkylpiperazines represent an interesting target in organic synthesis both for pharmaceutical or agrochemical applications and as a promising class of ligands in coordination chemistry. We report here a microwave‐enhanced synthesis of these compounds starting from non‐activated N‐alkyl aziridines in the presence of catalytic...

Decontamination is a critical and enabling capability to mitigate and, in the best cases, neutralize the threat of chemical warfare agents (CWAs) to human health and the environment. Well-established conventional decontamination methods will be described and compared to more recent approaches based on catalytic degradation, in the presence of nanos...

BACKGROUND The olive fruit fly (OFF), Bactrocera oleae (Rossi), is the main insect pest of olive trees worldwide. Legislation limits to the use of some synthetic larvicidal insecticides is leading to the development of new control options for preventive control of adult flies. In the present study, the biological activity of four short‐chain alipha...

A set of organic/inorganic layered material was obtained by functionalizing a montmorillonite containing bentonite natural clay with linear aliphatic C6 or C7 aldehydes through a cost-effective and technologically simple incipient-wetness deposition method. The solids were investigated by means of a multi-technique approach (X-ray Powder Diffractio...

The cytotoxicity of ionic liquids (ILs) has been receiving attention in the context of the biological and environmental impact of their vast field of applications. It has been ascertained that the cell membrane is the main target of ILs when they interact with microorganisms, cells and bacteria; nevertheless, studies at the micro- and nano-scale ai...

Simple ammonium ferrates are competent catalysts for the CO2 coupling with aziridines to yield 5‐substituted 1,3‐oxazolidin‐2‐ones. Good yields with remarkable selectivity are obtained under mild reaction conditions, room temperature, and atmospheric CO2 pressure, especially for non‐hindered N‐alkyl, N‐benzyl and N‐allyl aziridines, without the nee...

Soluble tetrabutylammonium ferrates, [TBA][FeX3Y] (TBA = ⁿBu4N) were synthetized by treating ferric salts (FeX3) with tetrabuthylammoniom halides. Their activity as a stand-alone catalyst in CO2 cycloaddition reactions to epoxides was assessed under solvent free and quite mild reaction conditions (CO2 pressures between 0.4 and 0.8 MPa) and TOF up t...

We have recently shown that simple ammonium ferrates are competent catalyst for the cycloaddition reaction of CO2 to epoxides under moderate reaction conditions (T = 100°C, P(CO2) = 0.8 MPa). We report here that ammonium zincates of general formulae [TBA]2 [ZnX4] (TBA = tetrabutylammonium), simply obtained by treating an ethanolic solution of an ap...

The cytotoxicity of Ionic Liquids (ILs) has been raising attention in the context of the biological and environmental impact of their vast field of applications. It is ascertained that the cell membrane is the main target of ILs when they interact with microorganisms, cells and bacteria; nevertheless, studies on the micro- and nanoscale aimed at be...

Binuclear iron oxo-bridged complexes have found much interest since the early 80’s as synthetic models for relevant biological molecules, catalysts and magnetic probes. In this work, a series of iron(III)bromide-based oxo-bridged complexes of Pyclen ligands was prepared, with the aim of investigating the peculiar iron-oxygen bond features in differ...

The development of alternative benign reaction conditions to perform multicomponent reactions is an interesting and desirable strategy to increase the sustainability of organic synthesis. In this paper, we report a new version of A3‐coupling MCR for the preparation of differently substituted propargylamines starting from aldehydes, alkynes and amin...

This article provides an overview (non-comprehensive) of the recent developments regarding pyridine-containing 12-membered tetraazamacrocycles with pyclen or Py2N2 backbones and their metal complexes from 2017 to the present. Firstly, the syntheses of newly described ligands and complexes with relevance to medicine are described. The second part de...

The review describes the most recently reported and efficient methods for the synthesis of heterocyclic compounds involving metal carbenes. In particular, copper, silver and gold carbenes, generated from suitable precursors, are involved in the synthesis of heterocyclic compounds through the formation of new carbon-heteroatom bonds.

Soluble tetrabutylammonium ferrates, [TBA][FeX3Y] (TBA = nBu4N) were synthetized by treating ferric salts (FeX3) with tetrabuthylammoniom halides. Their activity as a stand-alone catalyst in CO2 cycloaddition reactions to epoxides was assessed under solvent free and quite mild reaction conditions (CO2 pressures between 0.4 and 0.8 MPa) and TOF up t...

The implementation of innovative and environment-friendly control methods against the olive fruit fly, Bactrocera oleae, has attracted an ever-growing attention, especially after 2014, 2016 and 2019 when the Italian olive oil production suffered from qualitative and quantitative losses. In this aim, two series of solids were prepared: 1) copper(II)...

Interfering with the ability of pathogenic bacteria to import glucose may represent a new promising antibacterial strategy, especially for the treatment of infections occurring in diabetic and other hyperglycemic patients. Such patients are particularly susceptible to infections caused by a variety of bacteria, among which opportunistic pathogens l...

A soluble ferrate salt was synthetized by treating a novel protonated pyridine-containing macrocyclic ligand with iron(III) bromide. Its good activity as a stand-alone catalyst in CO2 cycloaddition reactions to epoxides was assessed. Good yields of cyclic organic carbonates were obtained, especially with terminal epoxides, under solvent-free reacti...

The reaction between epoxides and CO2 to yield cyclic carbonates is efficiently promoted under solvent‐free and relatively mild reaction conditions (0.5 mol % catalyst loading, 0.8 MPa, 125 °C) by zinc(II) complexes of pyridine containing macrocyclic ligands (Pc−L pyridinophanes). The zinc complexes have been fully characterized, including X‐ray st...

Two sets of unprecedented push-pull isoquinolines, characterized by an opposite "dipolar moment" with respect to the longitudinal axis of the molecule, have been prepared. The key step of the approach is the microwave-promoted domino imination/cycloisomerization of 2-alkynyl benzaldehydes in the presence of methanolic ammonia. Absorption spectra an...

Metal imido complexes, generally indicated as LnMNR, are considered key-intermediates in nitrene transfer reactions, which are efficient and atom-economic procedures for the synthesis of N-containing compounds. The isolation and characterization of catalytically active imido complexes are usually difficult tasks due to their high chemical reactivit...

The selective oxidation of different primary and secondary alcohols to carbonyl compounds by hydrogen peroxide was found to be catalyzed in conversion ranging from good to excellent by an iron(III) complex of a pyridine‐containing macrocyclic ligand (Pc‐L), without the need of any additive. The choice of the counteranion (Cl, Br, OTf) appeared to b...

A highly reactive and selective catalytic system comprising Cu(I) and a macrocyclic pyridine‐containing ligand (Pc−L) for the synthesis of 2‐(penta‐2,4‐dien‐1‐ylidene) 3‐oxoindolines from 4H‐furo[3,2‐b]indoles and diazoalkane is reported herein. The reaction sequence involves the initial formation of a copper‐carbene by Cu(I)‐catalyzed decompositio...

In this paper, we describe a new silver catalysed domino approach to 6‐substituted benzoxazino isoquinolines starting from 2‐alkynylbenzaldehydes and 1‐substituted‐(2‐aminophenyl)methanols. The strategy is characterized by good reaction yields, and can be performed at room temperature as well as under heating (conventional or dielectric) in differe...

In this paper, we describe the synthesis of neglected 1‐aminoisochromene derivatives starting from 2‐alkynylbenzaldehydes and electron‐poor anilines. The domino reaction is catalyzed by original [AgIPcL] complexes and occurs with complete regioselectivity under mild conditions. The approach well‐tolerates different aryl, heteroaryl, alkyl and cyclo...

Significance Understanding how carnivorous plants actuate leaf motion to capture their preys is an intriguing problem with potential applications for bio-inspired materials. Here, we show that bending of Drosera capensis leaves is programmed into its asymmetric cellular architecture and actuated by the action of growth hormones. A similar strategy...

A highly reactive and selective catalytic system comprising Fe(III) and macrocyclic pyridine‐containing ligands (Pc‐L) for alkene oxidation by using hydrogen peroxide is reported herein. Four new stable iron(III) complexes have been isolated and characterized. Importantly, depending on the anion of the iron(III) metal complex employed as catalyst,...

2-alkenyliden-indolin-3-ones were synthesised in high yields via a cascade reaction between 4H‑furo[3,2‑b]indoles and propargyl esters. The cascade sequence involves initial formation of a gold-carbenoid specie via cationic gold(I) catalysed 1,2-acyloxy migration of properly substituted propargyl esters followed by gold-carbenoid to furoindole addi...

In this paper, we describe the use of p‐TSA based Deep Eutectic Solvents (DESs) as alternative environmental‐friendly “active” solvents for the microwave‐mediated synthesis of 6‐substituted 3,4‐fused 2‐pyranones, and in particular isocoumarins, starting from 2‐alkynyl‐(hetero)arylcarboxylates. When the alkyne terminus bears a neutral or an electron...

The exceptionally frequent entries of alien pest are a major source of concern for the farmers who have to protect their crops from unknown insects, often without natural enemies in the new areas. A new pest belonging to the Molytinae family (Coleoptera: Curculionidae), tribe Hylobiini, reported as Aclees sp. cf.foveatus Voss, was recently introduc...

The reaction between N‐substituted‐2‐arylaziridines and CO2 is efficiently promoted by ruthenium(VI) imido porphyrin complexes and yields a mixture of 5‐aryl (A) and 4‐aryl (B) substituted oxazolidin‐2‐ones with a regioisomeric A/B ratio up to 99:1. Several oxazolidin‐2‐one molecules were synthesized at 100°C and 0.6 MPa of carbon dioxide by using...

The introduction of a pyridine moiety into the skeleton of a polyazamacrocyclic ligand affects both the thermodynamic properties and the coordination kinetics of the resulting metal complexes. These features have engendered a great interest of the scientific community in recent years. The field of application of pyridine-containing macrocyclic liga...

A catalytic system comprising copper(I) and macrocyclic pyridine-containing ligands (Pc-L) proves capable of promoting carbene SiH bond insertions using diazo compounds as the carbene source. This catalytic system showed broad scope and a remarkable robustness as indicated by high TON numbers (up to 30000). Moreover, the use of enynones as carbene...

The catalytic activity of the iron(III) C2 chiral porphyrin Fe(2)(OMe) in alkene cyclopropanation is herein reported. The catalyst promoted the reaction of differently substituted styrenes with diazo derivatives with trans-diastereoselectivities and enantioselectivities up to 99:1 and 87 %, respectively. In addition, high TON and TOF values (up to...

We report herein the synthesis of new pyridine-containing macrocyclic ligands (Pc-L) bearing a non-innocent pendant arm, by exploiting both chiral and functional properties of natural amino acids. The obtained macrocyclic ligands were employed to synthesize well-defined cationic silver(i) complexes that were shown to be competent catalysts for the...

Silver(I) complexes of pyiridine-containing macrocyclic ligands (Pc-L) have already been demonstrated as active catalysts for some domino and multicomponent reactions. Here, we report new chiral [AgI(Pc-L*)] cationic complexes that have been synthesized and fully characterized, including structural determination by single-crystal X-ray diffraction....

We report herein the synthesis of new glycoporphyrin ligands which bear a glucopyranoside derivative on each meso-aryl moiety of the porphyrin skeleton. The saccharide unit is directly conjugated to the porphyrin or a triazole spacer is placed between the carbohydrate and porphyrin ring. The obtained glycoporphyrin ligands were employed to synthesi...

The reactivity of various α-diazocarbonyl piperidine scaffolds, characterised by an increased molecular complexity, was tested with various RhII catalysts. The structure of the starting reagent is of relevance to the synthetic results. An unexpected dimerisation took place, starting from the simple piperidine scaffold, to give the hexahydrotetrazin...

Ar-BIANH2 bearing different substituents on the aryl rings have been synthesized in high yield by reduction of the corresponding bis(aryl)acenaphthenequinonediimine (Ar-BIAN) compounds. The structure of p-CH3C6H4-BIANH2 in the solid state was determined by X-ray diffraction. An exhaustive voltammetric investigation of the two parallel BIAN and BIAN...

The new silver catalysts (AGC) and (ATF) efficiently promote the ring closure reaction of 2-alkynylbenzaldehydes with primary and secondary alcohols.

An unprecedented reactivity of aryl azides toward alkynes is presented herein. The reaction performed well in the presence of 2 mol % of ruthenium porphyrin catalysts and afforded substituted indoles instead of triazoles. The procedure is particularly appealing for the synthesis of C3-functionalized indoles which bear EWG on the fragment coming fro...

This feature article provides an overview of the application of organic azides for the intermolecular amination of sp3 and sp2 C-H bonds. The catalytic activity of several metal complexes was reviewed underlining both synthetic and mechanistic aspects of the C-H amination. The majority of the aminated compounds reported in literature have been coll...

Two original macrocyclic silver(I)(pyridine-containing ligand) complexes [Ag(I)(Pc-L)] were synthesized and characterized. Their ability to catalyze the coupling among aldehydes, terminal alkynes and amines (A3-coupling) was demonstrated. The reaction could be performed under conventional as well as dielectric heating. The catalysts were effective...

This feature article provides an overview of the application of organic azides for the intermolecular amination of sp(3) and sp(2) C-H bonds. The catalytic activity of several metal complexes was reviewed underlining both synthetic and mechanistic aspects of the C-H amination. The majority of the aminated compounds reported in literature have been...

Continuous flow heterogeneous asymmetric cyclopropanations catalysed by supported hydrogen-bonded (SHB) chiral copper(i) complexes of pyridine containing tetraazamacrocyclic ligands Pc-L* using CO2 as a transport vector are described. The catalytic system showed high stability and good recyclability without loss of activity for at least 24 h in CO2...

Herein we report the catalytic activity of ruthenium porphyrin complexes to promote the amination of benzylic C–H bonds by aryl azides, yielding α- and β-amino esters. The catalytic methodology is also effective to synthesize two derivatives of methyl l-3-phenyllactate in order to convert one of them into the corresponding β-lactam. The catalytic e...

Compounds containing cyclopropane units play a crucial role in both synthetic and pharmaceutical chemistry due to high reactivity and biological properties of the three-membered ring.[1] Consequently, the interest of the research community in developing new methodologies to synthesise cyclopropanes is strongly increasing. Amongst the synthetic proc...

The synthesis of 3-substituted-1-alkoxyisochromenes starting from 2-alkynylbenzaldehydes and different alcohols is reported. The reaction is catalysed by a silver(I) complex with an original macrocyclic pyridine-containing ligand (Pc-L). The approach is characterised by absolute regioselectivity, mild reaction condition, good to excellent reaction...

A new chiral iron porphyrin-based catalyst performed α-methylstyrene stereoselective cyclopropanation with excellent yields (up to 99%), enantio- and diastereoselectivities (eetrans up to 87%, trans/cis ratios up to 99 : 1) and outstanding TON and TOF values (up to 20 000 and 120 000 h(-1) respectively).

The grafting of the preformed Pc-L* (pyridine containing macrocyclic ligands) copper(I) complexes on different ordered and non-ordered silicas, and their use, under heterogeneous batch conditions, as catalysts for the olefin cyclopropanation are reported. High yields (up to 99%) and good recyclability in halogen-free solvent reactions were obtained...

Shedding light on azides: [Ru(TPP)CO] (TPP=tetraphenyl porphyrin dianion), white light and O(2) were found to be a suitable catalyst combination to perform the annulation of several biaryl azides. The high chemoselectivity of the process allows the synthesis of phenanthridines and dihydrophenanthridines in good yield and purity.

New copper complexes of several thiosemicarbazones have been prepared and characterized. All complexes have been prepared by employing Cu (II) acetate hydrate, but analytical and spectroscopical data for the isolated complexes revealed that in most cases a reduction to copper (I) occurred. Cyclopropanation reactions of several olefins by ethyldiazo...

The synthesis and characterisation of copper(i) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*) and their use as catalysts in asymmetric cyclopropanation reactions are reported. All ligands and metal complexes were fully characterised, including crystal structures of some species determined by X-ray diffraction on single crystal...

Co(porphyrin) complexes promote an unusual reactivity of dihydronaphthalene towards several aryl azides. The reaction affords the benzylic amine of tetrahydronaphthalene instead yielding the amine of dihydronaphthalene as it normally happens in the presence of Ru(porphyrin)CO catalysts. The amination process occurs with the concomitant reduction of...

The one-pot reaction of diazo compounds with olefins represents a useful strategy to synthesise cyclopropanes, which are important both as starting materials for the synthesis of organic compounds and because of their intrinsic pharmaceutical properties. Herein we describe the catalytic activity of group 9 metal porphyrin complexes to cyclopropanat...

Benzylic amines are synthesized in yield up to 90% by the Ru(TPP)CO-catalyzed amination of both exocyclic and endocyclic benzylic C-H bonds. The choice of arylazides as nitrogen sources confers to the methodology a good sustainability due to the formation of molecular nitrogen as the only stoichiometric by-product. A preliminary mechanistic investi...

This paper describes the synthesis of allylic amines by aryl azides (ArN3) catalyzed by [Ru(TPP)CO] (TPP = dianion of tetraphenylporphyrin). The employment of aryl azides renders the methodol. sustainable as the formation of mol. nitrogen is the only stoichiometric byproduct. The isolation of catalytic intermediates and spectroscopic and kinetic st...

The synthesis and characterization of copper(I) complexes of the novel pyridine-containing macrocyclic ligand (PC-L) and their use as catalysts in the Henry reaction are reported. The pyridine-based 12-membered tetraaza macrocyclic (PC-L) ligand 1 can be obtained in good overall yield (85%) from commercially available starting materials. The Cu(I)...

The cover picture shows the Monte Eyehorn (2131 m), Italy. The cyclopropanation of olefins mediated by porphyrin complexes of group IX metals has been reviewed, and several methodologies affording cyclopropanes with good diastereo- and enantioselectivity have been described. The efficiency of porphyrin complexes to reduce the activation barrier (as...

A review of synthetic methodologies reported in the last five years that yield N-heterocyclic products by intramolecular cyclization of organic azides with a particular emphasis on transformations catalyzed by metal complexes is presented. These reactions have been classified according to the ring size of the formed heterocycle.© 2011 Bentham Scie...

Palladium 2,9-dimethylphenanthroline (neocuproine, Neoc) and 6,6'-dimethyl-2,2'-bipyridine (Me2bpy) complexes [LPdX2] (1a, L = Neoc, X = Cl; 1c, L = Neoc, X = Br; 1d, L = Neoc, X = I; 1e, L = Me2bpy, X = I) undergo redn. in reaction with CO, tentatively yielding Pd(I) dimers [L2Pd2X2(μ-CO)2] (3a, 3c-e). Whereas the Neoc dimers are insol. and were...

For Abstract see ChemInform Abstract in Full Text.

For Abstract see ChemInform Abstract in Full Text.

The polyoxometalate-based catalytic cyclopropanation of olefins by ethyl diazoacetate (EDA) is reported. The outstanding catalyst productivity (TONs up to 100,000) and the use of equimolar EDA/olefin ratio confer to the methodology a high sustainability. Preliminary mechanistic investigations are also discussed.

Polymeric membranes embedding a metal complex have been previously employed as reusable catalysts under relatively mild conditions. Herein, the first example of a polymeric catalytic membrane employed under very forcing conditions (160 °C and 5 MPa CO) is reported. The reaction investigated was the redn. of nitrobenzene to aniline by CO/H2O, catal...

The synthesis of new pinene-derived chiral cyclopropylamines and their use in the synthesis of the first asymmetric Alkyl-BIAN ligands (Alkyl-BIAN = bis-(alkylimino)acenaphthenequinone) are reported.

We report herein the synthesis of the porphyrins 5,10,15,20-tetrakis(4-carboxybiphenyl)-porphyrin (H2TCBP) and 5,10,15,20-tetrakis(4-carboxy-2,6-dimethylbiphenyl)porphyrin (H2TCDMBP) bearing diphenyl units on meso-positions, and of their cobalt and silver derivatives. The silver complexes of H2TCDMBP and of H2TCPP (H2TCPP = 5,10,15,20-tetrakis(4-ca...

Three "basket handle" porphyrins have been prepd. by condensation of tetrakis-(α,β,α,β-2-aminophenyl)porphyrin atropoisomer with 1,1'-binaphthyl, 2,2'-dimethoxy, -3,3'-dicarbonylchloride, -3,3'-diacetylchloride and -3,3'-dipropanoylchloride. The epoxidn. of styrene with the three iron catalysts, obtained after metalation of the free porphyrins,...

In this paper we report the prepn. of catalytic polymeric membranes having the complex [(N,N'-bis(3-tert-butyl-5-(heptadecafluorooctyl)salicylidene)-trans-1,2-cyclohexanediamine)Co] embedded into Hyflon AD60X, PES and PSf and their use in the cyclopropanation reaction of olefins with Et diazoacetate (EDA). A study of the reaction in the homogeneous...

Palladium-phenanthroline complexes catalyze both the nitroarene carbonylation reaction and the amine oxidative carbonylation reaction to give, depending on the conditions, carbamates and ureas. There is evidence that the key step in both processes is the amine carbonylation. Here, we show that when the reaction is run in methanol key intermediate c...

A novel ligand HL (1), N,2-bis(1-(2-oxo-2H-chromen-3-yl)ethylidene)hydrazinecarbothioamide was synthesized through the condensation of 3-acetyl-2H-chromen-2-one and hydrazinecarbothioamide. This ligand was used to prep. new transition metal complexes of Cu(II), Ni(II) and Co(II). Characterization of the HL (1) ligand and its complexes is also repor...

Nitrene transfer reactions represent a useful methodology to synthesize in a few steps high added-value compounds used as organic intermediates. Herein, we describe the catalytic activity of metal porphyrin complexes in a wide range of reactions such as C-H hydrocarbon amination and olefin aziridination to synthesize nitrogen containing molecules....

The complex Ru(TPP)(NAr)(2) inserts a nitrene group into allylic and benzylic C-H bonds and is the key intermediate in the ruthenium porphyrin-catalyzed amination of hydrocarbons by aryl azides.

New transition metal complexes of CoII, CuII, NiII and VIVO with the Schiff base, HL, 3-acetylcoumarin-N(4)-phenylthiosemicarbazone have been prepd. Characterization of the HL ligand and its complexes is also reported. Mass spectra and NMR assignments for the ligand, using COSY, NOESY homonuclear and HMQC and HMBC heteronuclear correlation techniqu...

Herein we report the one-pot synthesis of several N-heterocyclic compounds by rearrangement reactions of N-aryl-2-vinylaziridines. The optimization of the synthetic methodology employed allowed us to obtain differently substituted 2,5-dihydro-1H-benzo[b]azepines in good yields and purities. The relationship between the nature of the starting N-aryl...

Cobalt(II) complexes of chiral bis-binaphthyl porphyrins were prepd., and their catalytic activity in the asym. cyclopropanation of alkenes with Et diazoacetate was examd. Good yields and enantioselectivities (up to 90% ee) were obsd. with cis/trans ratios reaching 11:89. UV-vis and 1H NMR studies suggest that the axial nitrogen ligand N-methylimid...

The synthesis and characterisation of copper(i) complexes, including two crystal structures of the new chiral pyridine-containing macrocyclic ligands (PC-type), and their use as catalysts in asymmetric cyclopropanation reactions are reported.

CoII(tpp) catalyzes the reaction of arom. azides (ArN3) with nonactivated olefins to yield allylic amines or aziridines in moderate-to-good yields. The chemoselectivity of the catalytic reaction is particularly high. Depending on the substrate employed, allylic amines or aziridines can be obtained. The reaction mechanism was investigated, and the r...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

In this paper we report the prepn. of catalytic membranes having the complex Ru(4-(CF3)TPP)CO (1) (TPP = dianion of tetraphenylporphyrin) embedded in the perfluorinated polymer Hyflon AD60X and their use in the aziridination reaction of olefins by aryl azides. The heterogeneous membrane catalysts afforded high selectivities in aziridine (90-99%). I...

In this work, the ruthenium porphyrin complex Ru(4-(CF3)TPP)CO (1) (TPP = dianion of tetraphenylporphyrin) was entrapped into polymeric membranes during the phase inversion process to obtain new heterogeneous catalysts for aziridination reactions. In order to study the effect of the polymeric environment on the activity of the metallic complex, sym...

Aryl azides have been used as atom-efficient nitrene transfer reagents in the (porphyrin)ruthenium-catalyzed amination of olefins. Several azides, olefins and [Ru(porphyrin)CO] complexes were tested to investigate the scope and limits of the reaction. Quant. yields and short reaction times were achieved by using terminal olefins and aryl azides bea...

[Ru(CO)(porphyrin)] complexes have been found to catalyze the direct aziridination of conjugated dienes by aryl azides with high chemoselectivity, to provide N-aryl-2-vinylaziridines. To det. the scope of the reaction, several hydrocarbons and azides were tested. The reactions between 2,3-dimethylbuta-1,3-diene and aryl azides bearing electron-with...

The application of reductive carbonylation of nitroarenes to the synthesis of fine chems. is described. The review focuses on the results reported from 1996 onwards and is mainly divided in two parts, resp. describing the intra-mol. cyclization reactions of nitroarenes bearing in the ortho position a suitable functional group and the inter-mol. rea...

We report here the syntheses of two new metal complexes (M = Co, 2; M = Ru, 3) of the chiral porphyrin TmyrtP (1) (TmyrtP = dianion of the meso-tetrakis[(1R)-apopinen-2-yl]porphyrin). Both complexes exist as a mixt. of atropisomers. Complexes 2 and 3 activate arom. azides for the amination under mild conditions of unsatd. hydrocarbons. Even though...

The interaction of org. azides with transition metal complexes will be discussed with particular attention to the coordination modes of these mols. The stoichiometric reactions of org. azides with coordinated ligands will be considered and their use in amination reactions catalyzed by transition metal complexes will be discussed in detail. The util...

Palladium-phenanthroline complexes efficiently catalyze the reaction of nitroarenes with arylalkynes and CO to give 3-arylindoles by an ortho-C-H functionalization of the nitroarene ring. Both electron-withdrawing and electron-donating substituents are tolerated on the nitroarene, except for bromide and activated chloride. Nitroarenes bearing elect...

The application of the palladium-phenanthroline catalytic system to the carbonylation of nitrobenzene in the presence of aniline to afford diphenylurea has been investigated. The reaction is best performed with equimolar amounts of the two reagents. Use of higher concentrations of either aniline or nitrobenzene or an increase in temperature in the...

The reaction of Ru(TPP)CO (TPP = dianion of tetraphenylporphyrin) with 1-(p-nitrophenyl)-5-methyl-5-phenyl-1,2,3-triazoline yielded a D2-1,2,3-triazoline ruthenium(II) porphyrin complex, which is responsible for the catalyst deactivation in the aziridination reaction of a-methylstyrene by p-nitrophenyl azide. [on SciFinder (R)]

Co(acacen), 1, (acacen=2,11-dihydroxy-4,9-dimethyl-5,8-diaza-2,4,8,10-dodecatetraene dianion) was found to be a highly efficient catalyst for the allylic amination of non activated alkenes, using N-(p-toluensulfonyl)iminophenyliodinane (PhINTs) as nitrene precursor. This reactivity has been extended to the less reactive CâââH bond of toluene. Th...

A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investiga...

The synthesis of Ar,Ar'-BIAN ligands (Ar,Ar'-BIAN = bis(aryl)acenaphthenequinonediimine) having different aryl groups bound to the two nitrogen atoms is reported for the first time. The ligands were obtained by two different strategies: (i) by a transimination reaction starting from a symmetric Ar,Ar-BIAN ligand having aryl groups bearing strongly...

The allylic amination of unfunctionalized olefins by nitroarenes under CO pressure, catalyzed by Ru3(CO)12/Ph-BIAN (Ph-BIAN = bis(phenylimino)acenaphthenequinone) was extended to substrates with strongly electron-withdrawing groups on the nitroarene. Reaction of 1,4-dinitrobenzene selectively affords functionalization of only one nitro group, the o...

The new C2-symmetrical 1,2-diamine {N,N′-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]-1,2-ethanediamine}3 has been synthesized from commercial (1R)-(+)-camphor 1 and scrutinized as ligand in the oxidative biaryl coupling of naphthol derivatives. Under the optimal conditions employing a Cu(I)-3 triflate complex (10 mol%) in dichloroethane–...