New synthesis of benzo[1,2-b:4,5-b′]dithiophene (BDT)

Thiophene-containing polycondensed aromatic compounds are important source of functional organic materials for different applications. Within this class of molecules, benzo[1,2-b:4,5-b\u2032]dithiophene (BDT, figure 1) is recognized as one of the most successful building blocks in the synthesis of highly efficient photovoltaic and semiconducting materials.1 In fact the rigid and planar conjugated structure of BDT makes it attractive for achieving highly tunable molecular energy levels and optical band gaps as well as high hole mobilities. In recent years, benzannulation and thieannulation approaches, involving several steps, have been applied to the synthesis of BDT and of \uf070-extended thienoacenes,2 but the search of alternative easy access to this class of heterocycles is always a valuable synthetic target. We present here a new two-step synthesis of BDT, starting from 3-thiophene carbaldehyde as unique thiophene precursor. Although the second step of the synthesis needs to be optimized, this new methodology is certainly competitive to the classical approach3 which involves four steps, more expensive reagents and gives a comparable overall yield. In addition, the use of different hetero/aromatic aldehydes in the reaction with intermediate 2 gives access to a series of thiophene benzocondensed heterocycles

Non photochemical route to functionalized thiophene-based [7]helicenes

Helicenes are an intriguing class of ortho-annulated polycyclic aromatic or heteroaromatic compounds endowed with inherent chirality owing to the helical shape of their \uf070-conjugated system. These curved organic molecules provide unique opportunities for applications in manifold fields, including materials sciences, chiroptical devices, and asymmetric synthesis.1 Among helicenes, thiahelicenes are emerging as one of the most popular class of heterohelicenes thanks to their unique characteristics combining the electronic properties of oligothiophenes, with the chiroptical properties of helical shape molecules.2 For several years, we have been interested in the study of the synthesis and functionalization of thiahelicenes, such as tetrathiahelicene (7-TH) derivatives (Figure), that are configurationally stable and potentially very interesting for applications in optoelectronics,3 catalysis,4 and biology.5 Recently, we have developed a versatile non-photochemical procedure to prepare functionalized thiahelicenes, including a novel class of 7,8-diaryl substituted 7-TH compounds. This strategy involves the synthesis of chiral heterobiaryl derivatives as key intermediates, whose configurational stability have been elucidated in order to design an asymmetric version for the synthesis of enantioenriched thiahelicenes

Thiophene-based helicenes : eclectic scaffolds in organometallic chemistry

Helicenes are ortho-annulated polycyclic aromatic compounds, endowed with an inherently chiral \u3c0-conjugated system that are intensively studied in different areas of science.1 Among helicenes, thiophene-based helicenes are emerging as an intriguing and promising class of screw-shaped structures, thanks to the presence of the thiophene rings, which confer peculiar chemical, structural, and electronic features.2 For several years, we have been interested in the synthesis and functionalization of tetrathia[7]helicenes (7-TH, Figure 1), which are configurationally stable heterohelicenes, potentially very interesting for applications in optoelectronics,3 catalysis,4 and biology.5 In particular, transition metal-based 7-TH systems are an extremely appealing class of complexes, in which the coordination of metals with the \u3c0-helical ligand, bearing proper coordinating groups, provides unusual chiral architectures. Indeed, the selective functionalization of 2 and 13 positions of the 7-TH scaffold allows the introduction of a variety of substituents, including those with efficient coordinating ability (e.g. cyano, phosphane, phosphine oxide). In this communication we report our recent studies on the synthesis and characterization of 7-TH-based organometallic complexes, and their potential applications in optoelectronics and catalysis

Synthesis and characterization of a tetrathia[7]helicenebased rhenium(I) complex

Tetrathia[7]helicenes (7-TH), formed by thiophene and benzene rings ortho-fused in an alternating fashion, are emerging as one of the most popular class of chiral helical-shaped molecules, thanks to their peculiar electronic and chiroptical properties suitable for manifold applications in different areas of science.1 In particular, transition metal-based 7-TH systems are an extremely appealing class of complexes, in which the coordination of metals with the \uf070-helical ligand, bearing appropriate coordinating functionalities, provides original chiral architectures. Indeed, the effective functionalization of the \uf061-position(s) of the terminal thiophene ring(s) of the 7-TH scaffold allows the introduction of a variety of substituents, including those with efficient coordinating ability (e.g. cyano2, phosphane3, phosphine oxide4). For example, Rh(I)5 and Au(I)6 complexes based on 7-TH phosphanes have been successfully used in the homogenous transition metal catalysis. In our ongoing studies on 7-TH-based organometallic complexes, we have focused on a novel field of investigation concerning the development of rhenium-based polynuclear complexes containing 7-TH phosphine oxide ligands. In this communication, we describe the synthesis and the characterization of a novel dinuclear rhenium(I) complex (Figure 1), along with the elucidation of its tridimensional structure by single crystal X-ray diffraction studies

Axially chiral benzo[1,2-b:4,3-b’]dithiophene derivatives: a new route to tetrathiahelicenes

Thiophene-containing fused aromatic compounds represent an interesting class of \u3c0-conjugated systems in functional organic materials [1]. Among them, benzo[1,2-b:4,3-b\u2019]dithiophene (BDT) and its derivatives are by far the most widely studied, especially as units in mono and polydisperse oligomers in the field of the materials science [2], and as \u3c0-spacers in push-pull organic chromophores for photovoltaic applications [3]. Moreover, BDT is a key intermediate for the synthesis of inherently chiral helical systems such as tetrathia[7]helicenes 3 [4]. For all these reasons, BDT can be identified as a key starting molecule that, through a judicious functionalization of the \u3b1-positions of the thiophene rings, can allow access to more complex and interesting systems. Exploiting the experience acquired in our laboratories on the synthesis and functionalization of BDT derivatives [5,6], we have studied a novel and simple synthetic route to prepare bis(benzo[1,2-b:4,3-b\u2019]dithiophene) systems 2, through Pd-catalyzed cross coupling reactions, starting from bromides 1 (Figure 1).This strategy provides a convenient route to an interesting class of chiral atropisomeric heterobiaryl derivatives 2 with C2-symmetry, which can be used as starting reagents for an innovative non-photochemical synthesis of tetrathiahelicenes exploiting a Suzuki-Miyaura cross coupling and a Pd-catalyzed annulation with internal alkynes as key steps.. Asymmetric versions of this synthesis is under study

CHiral bis-benzo[1,2-b:4,3-b’]dithiophenes : synthesis and stereochemical properties

Thiophene-containing fused aromatic compounds are an interesting class of \u3c0-conjugated systems with applications in functional organic materials.1 Among them, benzo[1,2-b:4,3-b\u2019]dithiophene (BDT) and its derivatives are widely studied in the field of materials science,2 and for photovoltaic applications.3 Moreover, BDT is a key intermediate for the synthesis of inherently chiral helical systems such as tetrathia[7]helicenes.4 In our ongoing studies on the synthesis and functionalization of BDTs,5 we have developed a novel and convenient route to prepare an interesting class of chiral heterobiaryl bis(benzo[1,2-b:4,3-b\u2019]dithiophene) systems 2 and 3 (Figure 1). In this communication we will report the synthesis of compounds 2 and 3 along with the study of their chiroptical properties. Bromides 3 are also expected to have potential applications in asymmetric reactions, including the enantioselective synthesis of tetrathia[7]helicene derivatives

Exploring miR-9 Involvement in Ciona intestinalis Neural Development Using Peptide Nucleic Acids

The microRNAs are small RNAs that regulate gene expression at the post-transcriptional level and can be involved in the onset of neurodegenerative diseases and cancer. They are emerging as possible targets for antisense-based therapy, even though the in vivo stability of miRNA analogues is still questioned. We tested the ability of peptide nucleic acids, a novel class of nucleic acid mimics, to downregulate miR-9 in vivo in an invertebrate model organism, the ascidian Ciona intestinalis, by microinjection of antisense molecules in the eggs. It is known that miR-9 is a well-conserved microRNA in bilaterians and we found that it is expressed in epidermal sensory neurons of the tail in the larva of C. intestinalis. Larvae developed from injected eggs showed a reduced differentiation of tail neurons, confirming the possibility to use peptide nucleic acid PNA to downregulate miRNA in a whole organism. By identifying putative targets of miR-9, we discuss the role of this miRNA in the development of the peripheral nervous system of ascidians

Chiral bis(benzo[1,2-b:4,3-b’]dithiophene)s: synthesis and stereochemical characterization

Thiophene-containing fused aromatic compounds are an interesting class of \uf070-conjugated systems in functional organic materials (1). Among them, benzo[1,2-b:4,3-b\u2019]dithiophene (BDT) and its derivatives are widely studied, for instance as units in mono and polydisperse oligomers in the field of the materials science (2), and as \uf070-spacers in push-pull organic chromophores for photovoltaic applications (3). Furthermore, BDT is a key intermediate for the synthesis of inherently chiral helical systems such as tetrathia[7]helicenes (4).Thus, BDT can be identified as a key starting molecule, which can allow access to more complex and interesting systems through a judicious functionalization of the \uf061-positions of the thiophene rings. In our ongoing studies on the synthesis and functionalization of BDTs (5,6), we have developed a novel synthesis to prepare bis(benzo[1,2-b:4,3-b\u2019]dithiophene) systems 2, starting from bromides 1 (Figure 1).Compounds 2 belong to an interesting class of chiral atropisomeric heterobiaryl derivatives with C2-symmetry, which can be selectively functionalized into bromides 3. The chiroptical properties of both systems 2 and 3 have been fully elucidated by experimental and theoretical studies. On the other hand, enantiopure bromides 3 represent useful intermediates for the enantioselective synthesis of the corresponding tetrathiahelicene derivatives

A route to benzodithiophene systems by exploiting a ligand-free Suzuki-Miyaura coupling reaction in deep eutectic solvents

Benzo[1,2-b:4,3-b\u2019]dithiophene (BDT) and its derivatives belong to an interesting class of thiophene-based aromatic \uf070-conjugated compounds that are widely studied as functional organic materials inserted, for instance, as units in mono and polydisperse oligomers [1], or as \uf070-spacers in push-pull organic chromophores for photovoltaic applications [2]. Moreover, BDTs are key intermediates for the synthesis of inherent chiral tetrathia[7]helicenes, which are an attractive class of heterohelicenes with unique physicochemical and chiroptical properties due to their helix-like structure [3]. Thus, BDT is a key starting molecule which can allow access to more complex and interesting systems through a selective and judicious functionalization of the \uf061 and \uf062-positions of the terminal thiophene rings. Building on our recent studies on the synthesis and functionalization of BDTs [4], we questioned whether a novel class of 2,7-diarylsubstituted BDTs 1 (Figure 1) could be synthesized via a palladium-catalysed Suzuki-Miyaura reaction between heteroaryl halides 2 and organoboron derivatives 3 in Deep Eutectic Solvents (DESs), which have proven to be effective as sustainable and environmentally responsible reaction media in several transition-metal-catalyzed reactions [5].In this communication, we report our preliminary results on the preparation of diarylsubstituted BDTs 1, and discuss the substrate scope of the proposed protocol. Some of the compounds so far obtained display interesting photophysical properties, which are currently under investigation

Thiahelicene-grafted halloysite nanotubes: Characterization, biological studies and pH triggered release

A novel drug delivery nanosystem was here designed, linking thiahelicenes to halloysite nanotubes. Tetrathia[7]helicenes are very promising DNA intercalators, whose usage in biomedical field has been so far limited by their poor bioavailability. The study of appropriate drug delivery systems is needed to exploit helicenes as therapeutics. In this work, imine chemistry was adopted to covalently attach the bioactive compound and release it in acidic environments such as those surrounding tumour cells. To this aim, halloysite nanotubes were functionalized with (3-aminopropyl)triethoxysilane. The latter acted as linker providing NH2 groups to react with the formyl moiety of the thiahelicene derivative. The nanoconstruct preparation was studied in depth by surface-sensitive spectroscopies and angle-resolved X-ray absorption, to investigate the attachment mode, surface coverage and molecular orientation of the thiahelicene units. Release tests were carried out also in vitro on two tumour cell lines with different extracellular pH values. Mildly acidic pH conditions catalyzed the hydrolysis of the imine bond and promoted the cytotoxic compound release, which proved selective to slight pH differences, confirming the potential of this novel nanoconstruct