Front Cover: Facile Synthesis and Self‐Assembly of Zinc (2‐Diethoxyphosphorylethynyl)porphyrins (Eur. J. Inorg. Chem. 10/2019)

Rational design of aminoanthraquinones for colorimetric detection of heavy metal ions in aqueous solution

A family of water-soluble colorimetric chemosensors incorporating an anthraquinone signalling subunit functionalized with a polyamine chain that bears hydrophilic diethoxyphosphoryl moieties was prepared with the aim of assaying metal cations. The outstanding UV-Vis absorption properties of the 1-aminoanthraquinone chromophore allowed the efficient visual detection and quantification of copper(II) ions by chelators L(1)-L(3) in buffered aqueous solution. Moreover, the visible response of L(2) is not interfered by addition of large excesses of 13 common metal ions, whereas chemosensor L(3) produces also a color change in the presence of equimolar amounts of lead(II). Considering the 134 nm g…

Synthesis of 1,3-bis(trimethylcyclam) and 1,3-bis(trimethylcyclen) substituted benzenes

Pd-catalyzed amination of 1,3-dibromobenzene with N,N',N''-trimethylcyclam and N,N',N''-trimethylcyclen provided corresponding 1,3-bis(tetraazamacrocyclic) derivatives of benzene in 25-32% yields. The dependence of the products yields on the phosphine ligand applied (BINAP, DavePHOS) as well as on the stoichiometry of starting compounds was established. Scope and limitations for the synthesis of N-phenyl and N-(3-bromophenyl) derivatives of trimethylcyclam and trimethylcyclen were demonstrated.

Cover Picture: Palladium-Catalyzed Arylation of Linear and Cyclic Polyamines (Eur. J. Org. Chem. 2/2005)

The cover picture shows the model structures of four compounds among the hundred of arylated linear and cyclic polyamines prepared by palladium-catalyzed coupling of mono- and dihalogenoarenes with various aliphatic or aromatic polyamines. The reaction is strongly dependent on the nature and the concentration of the catalytic system, as well as the nature of the base. The competitive reaction between primary and secondary amines and the monoamination of dihalobenzenes have also been detailed in the article by R. Guilard et al. on p. 261 ff. In the following article by the same authors on p. 281 ff, the method has been applied to the synthesis of numerous nitrogen- and oxygen-containing macr…

Optical methods for the detection of heavy metal ions

The review covers an important area of the modern chemistry, namely, the detection of heavy metal ions using optical molecular detectors. The role of this method in metal ion detection and the physicochemical grounds of operation of chemosensors are discussed, and examples of detection of most abundant heavy metal ions and synthetic approaches to molecular detectors are presented. The immobilization of molecular detectors on solid substrates for the design of analytical sensor devices is described. The bibliography includes 178 references.

Immobilization of copper complexes with (1,10-phenanthrolinyl)phosphonates on titania supports for sustainable catalysis

Different strategies for the immobilization of copper complexes with 1,10-phenanthroline (phen) using the phosphonate anchoring group were investigated to prepare robust and porous heterogeneous catalysts. Homoleptic and heteroleptic copper(I) complexes with phen bearing the bis(trimethylsiloxy)phosphoryl anchoring group (Pphen-Si) at different positions of the phen backbone were prepared and covalently incorporated into titania (TiO2) xerogels by using the sol–gel process or grafted onto the surface of mesoporous TiO2 (SBET = 650 m2 g−1). Copper(I) bis(Pphen-Si) complexes were the only complexes that were successfully anchored onto the TiO2 surface because the heterogenization was often ac…

Arylation of polyamines by perfluoroarenes

Abstract The conditions of selective mono- and diarylation of diamines, and di- and triarylation of triamines by perfluoroarenes are described. The introduction of four perfluoroaryl groups in cyclam and two groups in dioxocyclam has been carried out.

Synthesis of a new family of bi- and polycyclic compounds via Pd-catalyzed amination of 1,7-di(3-bromobenzyl)cyclen

Abstract New bicyclic cryptand type compounds are synthesized by reacting 1,7-di(3-bromobenzyl)cyclen with 1 equiv of linear polyamines under dilute conditions using Pd-catalyzed amination. Bis(cyclen) and tris(cyclen) compounds containing linear polyamine linkers between benzylated cyclens are obtained by a similar procedure using different reaction conditions. Cyclization of these species via intramolecular catalytic diamination led to tri- and tetracyclic polyaza compounds.

Supramolecular chemistry of metalloporphyrins

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Palladium-catalyzed amination of aryl dibromides with secondary amines: synthetic and mechanistic aspects

Abstract Diaminobenzenes are obtained starting from m- and p-dibromobenzenes and secondary amines in the presence of Pd(dba)2/P(o-tolyl)3and sodium tert-butoxide in moderate to good yields. Reductive dehalogenation of aryl dibromides is a major side reaction under these conditions. The study of this reaction has shown that the formation of reductive dehalogenation products occurs according to two independent ways. The first one proceeds via the well-known β-hydride elimination from amido-coordinated palladium complexes. The second one involves the formation of hydrido palladium complexes from amino-coordinated derivatives. Although our results do not allow us to propose a detailed mechanist…

Palladium-Catalyzed Arylation of Linear and Cyclic Polyamines.

Synthetic protocols for the palladium-catalyzed arylation of various linear and cyclic polyamines and polyoxapolyamines has been worked out. Pd(0) and Pd(II) complexes with such phosphine ligands as dppf, BINAP, PPF-OMe, P(tBu) 3 , 2-ditert-butylphosphino- 1,1'-biphenyl have been explored in the catalytic amination reactions. Monoamination of chloro-, bromo-, and iodoarenes with di-, tri-, and tetraamines have been carried out, condi- tions for di- and polyarylation of linear polyamines have been elaborated. Successful aryla- tion of 1,4,7,10-tetraazacyclododecane (cyclene) and 1,4,8,11-tetraazacyclotetradecane (cy- clam) have been conducted. Intramolecular diamination of dihaloarenes such …

Palladium-catalyzed synthesis of aryl-substituted polyamine compounds from aryl halides

The reaction of polyamines having primary amino groups and 1,2-diaminoethane and/or 1,3-diaminopropane fragments with aryl bromides or iodides in the presence of sodium tert-butoxide and (dppf)PdCl2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene) proceeds selectively leading to monoaryl-substituted derivatives of polyamine. This reaction provides a convenient method of arylation of di-, tri- and tetraamine compounds. The Pd-catalyzed reactions of 1,3-diaminopropane and 3,3′-diaminodipropylamine with more reactive 1-bromonaphthalene can be used for the preparation of sym-dinaphthyl derivatives of these amines.

ChemInform Abstract: Palladium-Catalyzed Synthesis of Mono- and Diphosphorylated 1,10-Phenanthrolines.

A general protocol for the coupling of mono- and dihalo-1,10-phenanthrolines with diethyl phosphite is reported. This reaction proceeds smoothly in the presence of a Pd(OAc)2/dppf catalytic system and triethylamine as a base.

Pd-catalyzed amination in the synthesis of cyclen-based macrotricycles

Abstract Three approaches to three types of cyclen-based macrotricycles have been elaborated starting from trans-bis(3-bromobenzyl)cyclen. The macrotricycles were synthesized via Pd-catalyzed amination. The first approach employed consecutive macrocyclization and benzylation steps giving a cage-like tricycle. In the second, cyclen amino groups were Boc-protected prior to formation of the second and the third rings. In the third method, macrotricycles were synthesized according to a one-step procedure using diazacrown ethers.

Exploiting Palladium-Catalyzed Cross-Coupling for the Synthesis of 2-Aryl-Substituted 1-Aminocyclopropylphosphonates

A series of 2-aryl-substituted 1-aminocyclopropylphosphonates containing an additional remote phosphonate group have been synthesized starting from readily accessible dimethyl (1 R *,2 R *)-2-(4-bromophenyl)-1-formamidocyclopropylphosphonate using cross-coupling methodology. Different types of palladium-catalyzed reactions for carbon–carbon and carbon–phosphorus bond formation were realized. In each case the optimum conditions were found to obtain the desired products in high yield in both small- and large-scale experiments.

6-Polyamino-substituted quinolines: synthesis and multiple metal (CuII, HgIIand ZnII) monitoring in aqueous media

Chemoselective palladium-catalyzed arylation of polyamines with 6-bromoquinoline has been explored to prepare chelators for the detection of metal cations in aqueous media. The introduction of a single aromatic moiety into non-protected polyamine molecules was achieved using the commercially available Pd(dba)2/BINAP precatalyst to afford nitrogen chelators, in which the aromatic signalling unit is directly attached to the polyamine residue. Water-soluble receptors were then synthesized using N-alkylation of these polyamines by hydrophilic coordinating residues. By combining rich photophysical properties of the 6-aminoquinoline unit with a high coordination affinity of chelating polyamines a…

Cu(I) complexes with diethoxyphosphoryl-1,10-phenanthrolines in catalysis of C–C and C–heteroatom bonds formation

Abstract Diethoxyphosphoryl substituted 1,10-phenanthroline copper(I) complexes were tested as catalysts in the Sonogashira-type reaction, α-arylation of phosphoryl-stabilized C–H acids, C–N, C–P bond forming reactions (substitution reactions) and in the reaction of phenylacetylene and bis(pinacolato)diboron (addition reaction). The complexes demonstrate fairly high catalytic activity and in some cases their efficiency is superior to that of the parent Cu(phen)(PPh 3 )Br (phen = phenanthroline).

First highly distorted π-extended Fe(II) porphyrin – a unique model to elucidate factors affecting the electrochemical potentials

The preparation, X-ray crystal structure and electrochemistry of a new poly-substituted air-stable tetrabenzoporphyrin iron(II) bis-pyridine complex (1) is reported.

Palladium-Catalysed Amination of 1,8- and 1,5-Dichloroanthracenes and 1,8- and 1,5-Dichloroanthraquinones

Diamino derivatives of anthracene and anthraquinone have been synthesised by palladium-catalysed coupling of 1,8-dichloroanthracene and 1,8-dichloroanthraquinone with a wide range of aliphatic and aromatic primary and secondary amines. The use of polyamines gave rise to a large number of new nitrogen- and oxygen-containing macrocycles incorporating anthracene or anthraquinone moieties. The method has also been employed for the preparation of bismacrocycles in which two cyclam or azacrown units are linked together by an anthracene bridge through C(sp2)−N bonds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Palladium-Catalyzed Synthesis of Mono- and Diphosphorylated 1,10-Phenanthrolines

A general protocol for the coupling of mono- and dihalo-1,10-phenanthrolines with diethyl phosphite is reported. This reaction proceeds smoothly in the presence of a Pd(OAc)2/dppf catalytic system and triethylamine as a base.

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