Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks

• Zhan-Ting Li

Beilstein J. Org. Chem. 2015, 11, 2057–2071, doi:10.3762/bjoc.11.222

• sulfur-containing molecules and since the early 1990s, tetrathiafulvalene (TTF) supramolecular chemistry. Before I went to Odense, the group had developed a very useful method of in situ generation of TTF thiolate anion from cyanoethylated precursors, which greatly simplifies the modification of the TTF

• organic solvents. With hexafluorophosphate as the counterion, the catenanes were well-dissolved in acetonitrile, while with chloride, their solubility was poor. My stay in Odense initiated my research in supramolecular chemistry. For many years, I maintained interest in interlocked systems. TTF is also a

• the hydrogen-bonded aromatic amide and hydrazide sequences as a longstanding research area. With these sequences as a structural basis, we were able to investigate many interesting phenomena or concepts in supramolecular chemistry such as stimuli responsiveness, “sergeant–soldier effect”, and

The simple production of nonsymmetric quaterpyridines through Kröhnke pyridine synthesis

• Isabelle Sasaki,
• Jean-Claude Daran and
• Gérard Commenges

Beilstein J. Org. Chem. 2015, 11, 1781–1785, doi:10.3762/bjoc.11.193

• building blocks in metallo-supramolecular chemistry; however, their synthesis requires the preparation of sensitive building blocks. We present here three examples of nonsymmetric quaterpyridines that were easily obtained in yields of 70–85% by condensation of commercially available enones with 6-acetyl

• pyridine synthesis; Mannich bases; platinum; X-ray diffraction; Findings Polypyridines have been demonstrated to be useful building blocks in metallo-supramolecular chemistry [1][2][3]. In particular, polypyridines joined at the 2,6-position have the ability to accommodate different coordination numbers

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• -controlled gelation processes. TTF-based supramolecular chemistry in solution was thoroughly outlined in recent reviews of Jeppesen, Nielsen, and Becher (2004) [24], Iyoda, Hasegawa, and Miyake (2004) [25][26], Sallé and Zhang (2009) [27], and Martin (2009, 2012) [28][29]. However, limited examples of redox

Qualitative evaluation of regioselectivity in the formation of di- and tri-6-O-tritylates of α-cyclodextrin

• Keisuke Yoshikiyo,
• Yoshihisa Matsui and
• Tatsuyuki Yamamoto

Beilstein J. Org. Chem. 2015, 11, 1530–1540, doi:10.3762/bjoc.11.168

• supramolecular chemistry, as they allow the preparation of sophisticated concave molecules such as multi- or hetero-functionalized CD derivatives that are important intermediates for the preparation of enzyme mimics [1][2][3][4][5]. The tritylation of cyclodextrin (CD) has attracted much attention, since the

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• -responsive receptors for neutral and/or charged guest sensing applications have been prepared [18][19][20][21][22]. On this ground, chemosensors capable of recognizing anionic and/or cationic species constitute an important area of increasing research in supramolecular chemistry, considering the ubiquitous

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• many biologically active natural products such as macrocidin A (19) and B (20) [64], nostocyclyne A (21) [65], and in the turriane family of natural products 22–24 [66]. Cyclophanes are also applied in research areas such as pharmaceuticals [67][68], catalysis [69][70] and supramolecular chemistry [71

• attention of synthetic chemists. Liu and co-workers [166] have constructed the [10]paracyclophane 208 (skeleton of hirsutellones) via RCM. The 2,2’-bipyridine unit is an interesting building block due to its use in chelating ligands, as a binding agent and also a useful template in supramolecular chemistry

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• bispyrrolotetrathiafulvalenes (BPTTFs, 5) are useful structural motifs and have found widespread use in fields such as supramolecular chemistry and molecular electronics. Protocols enabling the synthesis of functionalised MPTTFs and BPTTFs are therefore of broad interest. Herein, we present the synthesis of a range of

• to the N-arylation of MPTTFs and BPTTFs using a variety of aryl halides. Keywords: heterocycles; protecting groups; sulfur chemistry; tetrathiafulvalene; Ullman coupling; Introduction Tetrathiafulvalene (TTF) derivatives are of considerable interest in the fields of supramolecular chemistry and

• materials with applications in supramolecular chemistry, molecular electronics and as sensors. The sequential, reversible oxidation of TTF (1) to its stable radical cation (2) and dication (3) states. Structures and possible substitution positions of MPTTFs (4) and BPTTFs (5). Large-scale synthesis of 6

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• control binding interaction towards a strong electron acceptor such as tetrafluorotetracyanoquinodimethane (F4-TCNQ) or a weaker electron acceptor such as 1,3-dinitrobenzene (m-DNB). Keywords: donor–acceptor interactions; glycoluril; molecular clips; supramolecular chemistry; tetrathiafulvalene

• -known access to molecular conductors [6][7] and TTF-acceptor assemblies [8][9], new concepts have been explored in the field of supramolecular chemistry using the TTF unit as a powerful electroactive building block [10]. Exploiting its peculiar electronic (two successive reversible oxidation steps

Multivalency as a chemical organization and action principle

• Rainer Haag

Beilstein J. Org. Chem. 2015, 11, 848–849, doi:10.3762/bjoc.11.94

• Rainer Haag Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany 10.3762/bjoc.11.94 Keywords: glycoarchitectures; supramolecular chemistry; multivalency; multivalent protein inhibitors; pathogen binding; Multivalency is a key principle in nature

Mechanical stability of bivalent transition metal complexes analyzed by single-molecule force spectroscopy

• Manuel Gensler,
• Christian Eidamshaus,
• Maurice Taszarek,
• Hans-Ulrich Reissig and
• Jürgen P. Rabe

Beilstein J. Org. Chem. 2015, 11, 817–827, doi:10.3762/bjoc.11.91

• important in biochemistry [1] and supramolecular chemistry [2], but still not fully understood on the level of individual non-covalent interactions [3]. Synthetic supramolecular systems are ideal for a quantitative analysis of multivalency on the level of single molecules, because specific ligand design can

Discrete multiporphyrin pseudorotaxane assemblies from di- and tetravalent porphyrin building blocks

• Mirko Lohse,
• Larissa K. S. von Krbek,
• Sebastian Radunz,
• Suresh Moorthy,
• Christoph A. Schalley and
• Stefan Hecht

Beilstein J. Org. Chem. 2015, 11, 748–762, doi:10.3762/bjoc.11.85

• ; pseudorotaxanes; Introduction Supramolecular chemistry [1], the chemistry “beyond the molecule“ [2], has immensely reshaped the concepts of chemistry by putting the intermolecular interaction into the focus. Different fields of chemistry, from materials [3][4][5][6] and analytical sciences [7][8][9][10][11][12

• being a mere spacer and scaffold connecting the binding sites, porphyrins also offer interesting physical and optical properties [51][52]. Therefore, they have played a pivotal role in supramolecular chemistry [53][54][55][56][57][58][59][60][61][62][63][64][65][66], for example as potential candidates

Multivalent polyglycerol supported imidazolidin-4-one organocatalysts for enantioselective Friedel–Crafts alkylations

• Tommaso Pecchioli,
• Manoj Kumar Muthyala,
• Rainer Haag and
• Mathias Christmann

Beilstein J. Org. Chem. 2015, 11, 730–738, doi:10.3762/bjoc.11.83

• and biochemistry [2] to supramolecular chemistry [3][4] and materials sciences [5]. However, applications in catalysis are still limited [6][7][8]. Recently, the use of polymeric support has stimulated the development of multivalent architectures for catalytic applications [9]. In general, both linear

Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting

• Christian Benkhäuser and
• Arne Lützen

Beilstein J. Org. Chem. 2015, 11, 693–700, doi:10.3762/bjoc.11.79

• social self-sorting manner as evidenced by NMR spectroscopy and mass spectrometry. Keywords: metal complexes; multivalency; self-assembly; self-sorting; supramolecular chemistry; Tröger's base; Introduction Self-assembly of defined aggregates from multicomponent mixtures through self-sorting effects

• has become an important issue in supramolecular chemistry [1][2][3][4][5]. Such self-sorting can either occur in a social self-discriminating or a narcissistic self-recognition manner (Scheme 1). In general, geometrical size and shape complementarity are used to ensure high-fidelity self-sorting. This

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• ; supramolecular chemistry; tetrathiafulvalene (TTF); thiophene; Introduction Since the discovery of the first organic metals and superconductors the field of electronic molecular materials has been largely dominated by derivatives of the organic donor tetrathiafulvalene (TTF) [1]. More than one thousand TTF

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

• Erdal Ertas,
• İlknur Demirtas and
• Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

• chemistry, materials chemistry, supramolecular chemistry and polymer chemistry. 1,8-Diketones have been demonstrated to be versatile starting materials for the synthesis of various challenging analogues of ET, possessing dithiin and thiophene moieties. This chemistry not only led to the production of the

Efficient deprotection of F-BODIPY derivatives: removal of BF₂ using Brønsted acids

• Mingfeng Yu,
• Joseph K.-H. Wong,
• Cyril Tang,
• Peter Turner,
• Matthew H. Todd and
• Peter J. Rutledge

Beilstein J. Org. Chem. 2015, 11, 37–41, doi:10.3762/bjoc.11.6

• facilitate chromatographic purification. The parent dipyrrins are more difficult to handle but have a range of potential applications in dye and porphyrin syntheses, metal ion coordination and supramolecular chemistry [12]. Methods to enable the functionalization of dipyrrins by temporarily complexing with

Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

• Lee Trollope,
• Dyanne L. Cruickshank,
• Terence Noonan,
• Susan A. Bourne,
• Milena Sorrenti,
• Laura Catenacci and
• Mino R. Caira

Beilstein J. Org. Chem. 2014, 10, 3136–3151, doi:10.3762/bjoc.10.331

• Lee Trollope Dyanne L. Cruickshank Terence Noonan Susan A. Bourne Milena Sorrenti Laura Catenacci Mino R. Caira Centre for Supramolecular Chemistry Research (CSCR), Department of Chemistry, University of Cape Town, Rondebosch 7701, South Africa Department of Drug Sciences, University of Pavia, Via

Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

• Joscha Vollmeyer,
• Friederike Eberhagen,
• Sigurd Höger and
• Stefan-S. Jester

Beilstein J. Org. Chem. 2014, 10, 2774–2782, doi:10.3762/bjoc.10.294

• ; solid/liquid interface; supramolecular surface patterning; template; Introduction One of the ultimate aims in supramolecular chemistry on solid surfaces is the formation of two-dimensional (2D) nanostructures that are capable of performing highly specific tasks as an effect of functional units that are

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

• Roman Matthessen,
• Jan Fransaer,
• Koen Binnemans and
• Dirk E. De Vos

Beilstein J. Org. Chem. 2014, 10, 2484–2500, doi:10.3762/bjoc.10.260

• are grateful to KU Leuven for support through the Methusalem grant CASAS, in the frame of IAP 7 Supramolecular Chemistry and Catalysis.

Molecular recognition of AT-DNA sequences by the induced CD pattern of dibenzotetraaza[14]annulene (DBTAA)–adenine derivatives

• Marijana Radić Stojković,
• Marko Škugor,
• Łukasz Dudek,
• Jarosław Grolik,
• Julita Eilmes and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2175–2185, doi:10.3762/bjoc.10.225

• /RNA sites [2][3], frequently relying upon new knowledge gained from supramolecular chemistry [4]. Among the large number of DNA/RNA sequences of biochemical interest, long homogeneous AT tracts have attracted significant attention as small molecule targets. An illustrative natural example can be found

Macrocyclic bis(ureas) as ligands for anion complexation

• Claudia Kretschmer,
• Gertrud Dittmann and
• Johannes Beck

Beilstein J. Org. Chem. 2014, 10, 1834–1839, doi:10.3762/bjoc.10.193

• rather weak complexing agent, the large ring of 2 binds anions with association constants up to log K = 7.93 for chloride ions. Keywords: anion binding; macrocyclic compounds; NMR spectra; supramolecular chemistry; template; urea; Introduction Supramolecular chemistry – the “chemistry beyond the

Influence of perylenediimide–pyrene supramolecular interactions on the stability of DNA-based hybrids: Importance of electrostatic complementarity

• Christian B. Winiger,
• Simon M. Langenegger,
• Oleg Khorev and
• Robert Häner

Beilstein J. Org. Chem. 2014, 10, 1589–1595, doi:10.3762/bjoc.10.164

• well as van der Waals, electrostatic and charge transfer interactions that can lead to a thermodynamically favourable association [8]. It is an important interaction in biological systems, drug receptor interactions, materials sciences, and supramolecular chemistry [8][9][10][11][12]. Such interactions

Molecular recognition of surface-immobilized carbohydrates by a synthetic lectin

• Melanie Rauschenberg,
• Eva-Corrina Fritz,
• Christian Schulz,
• Tobias Kaufmann and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2014, 10, 1354–1364, doi:10.3762/bjoc.10.138

• as drugs in various therapies and as recognition units in diagnostics and sensing. However, the development of synthetic lectins poses a phenomenal challenge for supramolecular chemistry [37] because a carbohydrate receptor in order to be useful must not only compete with the strong hydration of

• (SFB 858). This work was supported by COST CM1005 “Supramolecular Chemistry in Water”.

Homochiral BINOL-based macrocycles with π-electron-rich, electron-withdrawing or extended spacing units as receptors for C₆₀

• Marco Caricato,
• Silvia Díez González,
• Idoia Arandia Ariño and
• Dario Pasini

Beilstein J. Org. Chem. 2014, 10, 1308–1316, doi:10.3762/bjoc.10.132

• ; supramolecular chemistry; Introduction Shape persistent macrocycles are carbon-based nanomaterials and are more and more in demand. They enrich the molecular toolkit available to a variety of disciplines, e.g., supramolecular chemistry and materials science [1][2][3][4]. Shape persistency properties are

Synthesis, characterization and DNA interaction studies of new triptycene derivatives

• Sourav Chakraborty,
• Snehasish Mondal,
• Rina Kumari,
• Sourav Bhowmick,
• Prolay Das and
• Neeladri Das

Beilstein J. Org. Chem. 2014, 10, 1290–1298, doi:10.3762/bjoc.10.130

• organic molecules having terminal ethynyl functional groups are very useful synthons for the design of interesting materials in polymer and supramolecular chemistry [20][21][22][23][24][25]. Herein we report, the syntheses of 2,6,14- and 2,7,14-triazido and 2,6,14- and 2,7,14-triethynyl substituted

• interaction of triptycene derivatives with DNA in more detail, and the use of triptycene derivatives as building blocks in supramolecular chemistry. Experimental Methods of preparation of compounds 1–8 and their characterization data are given in Supporting Information File 1. Biological studies General