1,10-Phenanthroline: A versatile ligand to promote copper-catalyzed cascade reactions

Ligand-promoted copper-catalyzed cascade reactions have become a robust tool for the synthesis of cyclic compounds. Although numerous ligands have been developed, this review focuses on the introduction of commercially available 1,10-phenanthroline-promoted copper-catalyzed cascade reactions in recent years. Moreover, based on original articles, this review highlights product yields in the presence and absence of the ligand, and the possible mechanistic role of the ‘copper/1,10-phenanthroline’ catalytic system.     

New versatile building block for the construction of tetrathiafulvalene-based donor-acceptor systems

[reaction: see text] A new dissymmetrical tetrathiafulvalene (TTF) derivative 1 was synthesized as a versatile building block to reach TTF-based donor-acceptor assemblies incorporating C(60) in triad C(60)-TTF-C(60) 2 and/or p-benzoquinone (Q) in fused dyad Q-TTF 3 and triad Q-TTF-C(60) 4.     

Amidetriazole: a versatile building block for construction of oxyanion anion receptors

The design and synthesis of efficient receptors for tetrahedral oxyanions is an emerging field in supramolecular chemistry. Herein, we have developed a urea-like anion-recognizing motif, amidetriazole, which can be easily synthesized and derived and shows good solubility. A series of simple acyclic receptors were designed and synthesized to confirm the potential of amidetriazole for the construction of tetrahedral oxyanion receptors. This molecular platform can be used extensively for the construction of numerous receptor systems appended with functional groups, which opens the way to many applications in the field of supramolecular chemistry.     

A versatile building block for pyrazole-pyrrole hybrid macrocycles

This contribution describes the synthesis of a novel pyrazole-pyrrole building block and its use in the formation of a non-aromatic, Schiff base-type macrocycle incorporating a chromophore and H-bonding donor and acceptor functionalities inside and outside of the macrocycle, which makes it predestined for molecular recognition systems.     

Chelating dialkoxide titanium complex: a versatile building block for the construction of heterometallic derivatives

The heterometallic complex [TiCp*(O(2)Bz)(2)AlMe(2)] (2) has been synthesised by reaction of [TiCp*(O(2)Bz)(OBzOH)] (1) with AlMe(3) (Cp*=eta(5)-C(5)Me(5); Bz=benzyl). Complex 1 reacts with HOTf to yield the cationic derivative [TiCp*(OBzOH)(2)]OTf (3) (HOTf=HSO(3)CF(3)). Compound 3 reacts with [{M(mu-OH)(cod)}(2)] (M=Rh, Ir; cod=cyclooctadiene) to render the early-late heterometallic complexes [TiCp*(O(2)Bz)(2){M(cod)}(2)]OTf (M=Rh (4); Ir (5)). The molecular structure of complex 4 has been established by single-crystal X-ray diffraction studies.     

Isocorannulenofuran: a versatile building block for the synthesis of large buckybowls

Isocorannulenofuran, synthesized in two steps from accessible bromocorannulene, gives Diels-Alder adducts with benzynes which can be deoxygenated to produce large polycyclic aromatic hydrocarbons (PAHs) combining the bowl-shaped corannulene subunit with planar fragments. [reaction: see text]     

Ferrocenylpyrazole—A versatile building block for hydrogen-bonded organometallic supramolecular assemblies

The crystal architectures of 5-ferrocenylpyrazole (1) and its metal complexes were investigated. Compound 1 can form non-solvated and chloroform-solvated crystals. In both cases, 1 forms a zigzag one-dimensional architecture via NH?N hydrogen bonds. The hydrogen bond exhibits a twofold disorder, which was shown to be static by solid-state ¹³C NMR. In the solvated crystal, the chloroform is released at 415 K, associated with melting of the crystal. The reaction of 1 with metal salts provided metal-centered ferrocenyl clusters [Zn(NO₃)₂(1)₄] (4), [Co(NO₃)₂(1)₄] (5), [CoCl₂(1)₄] (6), [Zn(NCS)₂(1)₂] (7), cis-[Pt(NH₃)₂(1)₂](PF₆)₂ (8), and trans-[Pt(NH₃)₂(1)₄](PF₆)₂ (9). In all of these complexes, 1 acts as a monodentate ligand. In 4, 5, and 7, the multinuclear units are joined via hydrogen bonds to form supramolecular chains. Two polymorphs were found for the crystals of 4. Both are composed of the same hydrogen-bonded chains, but their arrangements are different. 5-Ferrocenyl-1-tritylpyrazole (2) and 4-ferrocenyl-1-methylpyrazole (3) were also crystallographically characterized.     

Synthesis of a versatile multifunctional building block for the construction of polyketide natural products containing ethyl side-chains

The synthesis of a multifunctional building block for polyketide construction and several subsequent reactions are presented.     

Synthesis of a versatile pentacyclic building block for organic electronics

A new pentacyclic building block, benzodibenzofuranquinone (BDBFQ), is synthesized in a single step from the inexpensive and readily available feedstocks chloranil and 3‐bromophenol. This versatile repeat unit is incorporated into a series of conjugated materials as either the redox active quinone form or as an electron‐rich dialkylated benzodibenzofuran (BDBF) unit. To illustrate the performance that can be obtained from these systems, optical and electrochemical properties were studied via UV–vis–NIR spectroscopy and cyclic voltammetry. Thin‐film morphology was characterized via grazing incidence wide‐angle X‐ray scattering with thin‐film field‐effect transistor measurements further demonstrating the utility of this system. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2618–2628     

Metal-complex/DNA conjugates: a versatile building block for DNA nanoarrays

The use of DNA networks as templates for forming nanoarrays of metallic centres shows an exciting potential to generate addressable nanostructures. Inorganic units can be photoactive, electroactive and/or can possess magnetic and catalytic properties and can adopt different spatial arrangements due to their varied coordination nature. All these properties influence both the structure and function of passive DNA scaffolds and provide DNA nanostructures as a new platform for new materials in emerging technologies, such as nanotechnology, biosensing or biocomputing.     

5,5'-Diamino-2,2'-bipyridine: a versatile building block for the synthesis of bipyridine/catechol ligands that form homo- and heteronuclear helicates

Herein we present an improved synthesis of 5,5'-diamino-2,2'-bipyridine (1) starting from the pyrrole-protected aminopyridine 4. By standard reactions 1 can easily be transformed into the imine- or amide-bridged dicatechol-bipyridine ligands L1-H4 and L2-H4. Whereas ligand L1 readily forms homodinuclear helicates [(L1)3Ti2]4-, the attempted formation of mono-, tri-, or even oligonuclear coordination compounds from this ligand did not work. However, the amide-connected ligand L2 affords mononuclear ([(L2-H4)PdCl2], [(L2-H4)3Zn]2+), dinuclear ([(L2)3Ti2]4-), and heterotrinuclear coordination compounds ([(L2)3Ti2Zn]2-).     

2,3-Dichloroquinoxaline as a versatile building block for heteroaromatic nucleophilic substitution: A review of the last decade

Nucleophilic aromatic substitution (SNAr) is a class of reaction that has become very important over time. This type of transformation usually proceeds without the use of metal catalysts, making it very important for pharmaceutical and industrial purposes. Nevertheless, in order to obtain the desired substituted product, activated substrates are required to allow SNAr reactions under mild conditions. In this context, quinoxaline derivatives are one class of N-heteroarenes that has attracted great attention from the scientific community because of the large variety of applications for their derivatives in many fields, such as biological and technological areas. There are several reported methods for the synthesis of quinoxaline derivatives. Nonetheless, reactions of 2,3-dichloroquinoxaline (DCQX) with nucleophilic species has become a viable alternative because of the possibility to form new carbon-heteroatom bonds (e.g. CO, CN, and CS) directly at C2 and/or C3 positions of the quinoxaline moiety. This current review brings an overview of the last decade on the remarkable versatility of DCQX as a substrate for SNAr reactions. Herein, we show several examples in which DCQX reacts with N-, O-, S-, P- and C-nucleophiles, including controlled processes for the selective formation of mono- and disubstituted substrates. Almost all polyfunctionalized quinoxalines synthesized using this approach have shown applications in different areas such as in biological and technological fields.     

Tricyanometalate molecular chemistry: A type of versatile building blocks for the construction of cyano-bridged molecular architectures

Cyano-bridged molecule-based magnetic materials with reduced dimensionality, such as single-molecule magnets (SMMs) and single-chain magnets (SCMs), have attracted great research interest during the last decade. Among the cyano-based molecular precursors with ample coordinating capability, we note the ability of the tricyanometalate to link various metal ions lead to a wide diversity of structural architectures ranging from discrete polynuclear complexes to various one-dimensional (1D) assemblies. Some of them are promising cyano-bridged SMMs and SCMs. The use of capping tridentate organic ligands results in a number of clusters containing di-, tri-, tetra-, penta-, hexa-, octa-, fourteen-nuclear and various 1D metal-cyanide molecular architectures. Here we review the structural topologies of these complexes and their related magnetic properties, highlight typical examples, and point out the main possible directions that remain to be developed in this field. From the crystal engineering point of view, the compounds reviewed here should provide useful information for further design and investigation on this elusive class of cyano-bridged SMMs and SCMs.     

A stable fullerene-azide building block for the construction of a fullerene-porphyrin conjugate

A stable C₆₀ derivative bearing an azide functional group was prepared and used as a building block under the copper-mediated Huisgen 1,3-dipolar cycloaddition conditions for the preparation of a fullerene-porphyrin conjugate.     

Hydrogen-bonded ionic liquid crystals: pyridinylmethylimidazolium as a versatile building block

Utilizing hydrogen bonding between pyridine and benzoic acids, hydrogen-bonded ionic liquid crystals were prepared from pyridinylmethylimidazolium and alkoxy-substituted benzoic acids. Depending on the number of alkoxy substituents, smectic C (SmC), rectangular columnar (Col_r), and cubic (Cub) phases were obtained from mono-, di-, and tri-substituted benzoic acids, respectively. These phases were investigated with X-ray diffraction, differential scanning calorimeter, and polarized optical microscopy.     

A cyclic glucosyl ceramide acceptor as a versatile building block for complex ganglioside synthesis

A cyclic glucosyl ceramide (GlcCer) acceptor has been developed as a versatile building block for the synthesis of complex ganglioside. A macrocyclic GlcCer acceptor, which was the product of intramolecular glycosylation between glucose and ceramide, exhibited high reactivity during the coupling reactions with a variety of complex oligosaccharyl donors, thereby furnishing the corresponding ganglioside frameworks in high yields.     

4-Trichloroacetyl-1,2,3-triazoles: A versatile building block for rapid assessment of carbohydrazides and rufinamide derivatives

This work reports the synthesis of a series of (1H-1,2,3-triazol-4-yl)carbohydrazides (2), which were obtained from 4-trichloroacetyl-1H-1,2,3-triazoles (1). Triazoles 1 were synthesized by 1,3-dipolar cycloaddition reaction, starting from 4-alkoxy-1,1,1-trichloroalk-3-en-2-ones and benzyl azides and easily (15 min) converted to 2 by reaction with hydrazine hydrate (73–82% yield). Carbohydrazides 2 proved to be a versatile building block for constructing a series of fluorinated heterocycles analogous to rufinamide, i.e., 1H-1,2,3-triazol-4-yl-1,3,4-oxadiazoles, a pyrrole derivative, and a 2-pyrazoline, through [4+1]–, [1+4]–, and [3+2]–cyclocondensation reactions, respectively. Finally, and according to the Lipinski’s rule of five, 2,6-difluorobenzylated 1,2,3-triazoles can be considered as potential candidates for further biological activity assays.     

Reversible supramolecular functionalization of surfaces: terpyridine ligands as versatile building blocks for noncovalent architectures

We report on the reversible and selective functionalization of surfaces by utilizing supramolecular building blocks. The reversible formation of terpyridine bis-complexes, based on a terpyridine ligand-functionalized monolayer, is used as a versatile supramolecular binding motif. Thereby, click chemistry was applied to covalently bind an acetylene functionalized Fe(II) bis-complex onto azide-terminated self-assembled monolayers. By decomplexation of the formed supramolecular complex, the ligand modified monolayer could be obtained. These monolayers were subsequently used for additional complexation reactions, resulting in the reversible functionalization of the substrates. The proper choice of the coordinating transition metal ions allows the tuning of the binding strength, as well as the physicochemical properties of the formed complexes and thus an engineering of the surface properties.     

Triazole: a unique building block for the construction of functional materials

Over the past 50 years, numerous roads towards carbon-based materials have been explored, all of them being paved using mainly one functional group as the brick: acetylene. The acetylene group, or the carbon-carbon triple bond, is one of the oldest and simplest functional groups in chemistry, and although not present in any of the naturally occurring carbon allotropes, it is an essential tool to access their synthetic carbon-rich family. In general, two strategies towards the synthesis of π-conjugated carbon-rich structures can be employed: (a) either the acetylene group serves as a building block to access acetylene-derived structures or (b) it serves as a synthetic tool to provide other, usually benzenoid, structures. The recently discovered copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction, however, represents a new powerful alternative: it transforms the acetylene group into a five-membered heteroaromatic 1H-1,2,3-triazole (triazole) ring and this gives rise to new opportunities. Compared with all-carbon aromatic non-functional rings, the triazole ring possesses three nitrogen atoms and, thus, can serve as a ligand to coordinate metals, or as a hydrogen bond acceptor and donor. This Feature Article summarises examples of using the triazole ring to construct conjugation- and/or function-related heteroaromatic materials, such as tuneable multichromophoric covalent ensembles, macrocyclic receptors or responsive foldamers. These recent examples, which open a new sub-field within organic materials, started to appear only few years ago and represent "a few more bricks" on the road to carbon-rich functional materials.