Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• ]. In addition to anilino groups, a myriad of donor entities, including urea-substituted phenyl groups [18][19], carbazoles [20], phenothiazines [21][22], thiophenes [23][24][25][26], tetrathiafulvalenes (TTFs) [27], extended TTFs [28], ferrocenes [27][29][30][31][32][33][34][35][36][37][38][39][40][41

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

• Aya Yoshimura,
• Hitoshi Kimura,
• Kohei Kagawa,
• Mayuka Yoshioka,
• Toshiki Itou,
• Dhananjayan Vasu,
• Takashi Shirahata,
• Hideki Yorimitsu and
• Yohji Misaki

Beilstein J. Org. Chem. 2020, 16, 974–981, doi:10.3762/bjoc.16.86

• Abstract Novel multistage redox tetrathiafulvalenes (TTFs) bearing 6-aryl-1,4-dithiafulvene moieties were synthesized by palladium-catalyzed direct C–H arylation. In the presence of a catalytic amount of Pd(OAc)2, P(t-Bu3)·HBF4, and an excess of Cs2CO3, the C–H arylation of TTF with several aryl bromides

• systems; electrochemical properties; extended π-conjugation; digital simulation analysis; tetrathiafulvalene; Introduction Tetrathiafulvalenes (TTFs) with extended π-conjugation have attracted attention as possible components of functional materials, such as molecular conductors, field-effect transistors

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• contemporary research challenge. Tetrathiafulvalenes (TTFs) are one of the most versatile and widely used molecular redox switches to generate and control molecular motion. TTF can easily be implemented as functional unit into molecular and supramolecular structures and can be reversibly oxidized to a stable

[2.2]Paracyclophane derivatives containing tetrathiafulvalene moieties

• Laura G. Sarbu,
• Lucian G. Bahrin,
• Peter G. Jones,
• Lucian M. Birsa and
• Henning Hopf

Beilstein J. Org. Chem. 2015, 11, 1917–1921, doi:10.3762/bjoc.11.207

• -dithiolium salts; [2.2]paracyclophane; regioselective bromination; stereoisomers; tetrathiafulvalenes; Introduction Tetrathiafulvalene (TTF) and its derivatives have been extensively studied with respect to their applications as organic metals and superconductors [1][2]. These properties are a consequence

• are known to provide tetrathiafulvalenes under specific conditions [11][12][13]. The synthetic strategy for the incorporation of the 1,3-dithiol-2-ylium ring in the [2.2]paracyclophane framework involves a three-step reaction sequence, starting from 4-acetyl[2.2]paracyclophane (1) (Scheme 1). The

• field (ca. 180 ppm) which corresponds to the electron-deficient C-2 atom. 1,3-Dithiolium salts are valuable precursors for tetrathiafulvalenes. There are two main synthetic approaches that are mainly based on the exploitation of the electron-deficient character of the C-2 carbon atom. One of these

Synthesis and spectroscopic properties of β-triazoloporphyrin–xanthone dyads

• Dileep Kumar Singh and
• Mahendra Nath

Beilstein J. Org. Chem. 2015, 11, 1434–1440, doi:10.3762/bjoc.11.155

• –tetrathiafulvalenes [14], porphyrin–cyanines [15], porphyrin–carotenes [16], porphyrin–arene diimide [17] and porphyrin–fluorocene or rhodamine [18] have also been synthesized in which the porphyrin unit acts as an electron acceptor. Recently, the 1,2,3-triazole scaffold has been successfully employed to connect

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

• Shintaro Iwamoto,
• Yuu Inatomi,
• Daisuke Ogi,
• Satoshi Shibayama,
• Yukiko Murakami,
• Minami Kato,
• Kazuyuki Takahashi,
• Kazuyoshi Tanaka,
• Nobuhiko Hojo and
• Yohji Misaki

Beilstein J. Org. Chem. 2015, 11, 1136–1147, doi:10.3762/bjoc.11.128

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

• the two cases where both solvents were used (5c and 5f). We expect that further optimisation of these reactions can be achieved using microwave or larger scale conditions, and investigations are currently underway in our laboratory. Conclusion Pyrrole-annelated tetrathiafulvalenes (MPTTFs and BPTTFs

Regioselective synthesis of chiral dimethyl-bis(ethylenedithio)tetrathiafulvalene sulfones

• Flavia Pop and
• Narcis Avarvari

Beilstein J. Org. Chem. 2015, 11, 1105–1111, doi:10.3762/bjoc.11.124

• conformation. Cyclic voltammetry measurements indicate fully reversible oxidation in radical cation and dication species. Keywords: chirality; crystal structures; molecular materials; sulfones; tetrathiafulvalenes; Introduction Chiral tetrathiafulvalene (TTF) derivatives have been addressed for the first

Donor–acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes

• Xiaofeng Lu,
• Jibin Sun,
• Shangxi Zhang,
• Longfei Ma,
• Lei Liu,
• Hui Qi,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 1043–1051, doi:10.3762/bjoc.11.117

Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

• Vladimir A. Azov,
• Diana Janott,
• Dirk Schlüter and
• Matthias Zeller

Beilstein J. Org. Chem. 2015, 11, 860–868, doi:10.3762/bjoc.11.96

• ; pyrrolotetrathiafulvalene; Ullmann-type coupling; X-ray crystallography; Introduction For the last four decades tetrathiafulvalenes [1][2] (Figure 1) 1 have been the subject of extensive studies due to their outstanding electron-donating properties and ability to induce reversible electrochemically-induced switching

• different analytical methods and X-ray crystallography. Experimental Copper-catalyzed N-arylation reaction of monopyrrolo-tetrathiafulvalenes, general procedure. The reaction was performed in a similar manner as described before [22]. A heavy walled Schlenk tube with a wide bore Teflon screw stopcock was

• = 0.86 V, E1/2ox3 = 1.77 V. Molecular structures of tetrathiafulvalenes 1, bis-pyrrolotetrathiafulvalenes 2 and monopyrrolotetrathiafulvalenes 3. Copper(I) ligands 9a and 9b. UV–vis spectra of compounds 4a,c–f (CH2Cl2, c = 4 × 10−5 M). Cyclic voltammograms of compounds 4a,c [22] and 4d–f (plotted vs SCE

Copper ion salts of arylthiotetrathiafulvalenes: synthesis, structure diversity and magnetic properties

• Longfei Ma,
• Jibin Sun,
• Xiaofeng Lu,
• Shangxi Zhang,
• Hui Qi,
• Lei Liu,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 850–859, doi:10.3762/bjoc.11.95

• : antiferromagnetic interaction; arylthio-substituted tetrathiafulvalenes; charge-transfer; crystal structure; magnetic property; Introduction Since firstly synthesized in 1970s [1], tetrathiafulvalene (TTF) and its derivatives have been intensively studied to explore functional organic materials [2]. Inspired by

• . Chemical structures of arylthio-substituted tetrathiafulvalenes (1–7). Electrochemical data of TTFs in this report.a Preparation, composition, yield, and appearance of the salts.a Selected bond lengths, calculated charge, and conformations of TTFs. Supporting Information Supporting Information File 347

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• Olivier Jeannin Frederic Barriere Marc Fourmigue Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes I, Campus de Beaulieu, 35042 Rennes, France 10.3762/bjoc.11.73 Abstract A series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron

• tetrathiafulvalenes functionalized by electron-withdrawing groups (EWG) are less documented, essentially because the presence of such substituents as halogen, acyl, ester, amide or nitrile on the TTF redox core dramatically increases its oxidation potential and destabilizes the radical cation form. This strong anodic

• accordingly, several tetrathiafulvalenes bearing only one or two ester [10], nitrile [11][12][13][14], amide [7][15][16][17], thioamide [18][19][20], or halogen [5] substituents were successfully engaged in radical cation salts by electrocrystallization, with intermolecular hydrogen [21][22][23] of halogen

The Ugi four-component reaction as a concise modular synthetic tool for photo-induced electron transfer donor-anthraquinone dyads

• Sarah Bay,
• Gamall Makhloufi,
• Christoph Janiak and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 1006–1016, doi:10.3762/bjoc.10.100

• ]. This photo-induced electron transfer (PET) [30][31][32][33][34] has been investigated with donors such as porphyrines, polycyclic aromatic hydrocarbons, perylenediimides and (oligo)thiophenes [35][36], tetrathiafulvalenes [37], as well as phenothiazine and its derivatives [22][38][39][40]. The latter

Hybrid super electron donors – preparation and reactivity

• Jean Garnier,
• Douglas W. Thomson,
• Shengze Zhou,
• Phillip I. Jolly,
• Leonard E. A. Berlouis and
• John A. Murphy

Beilstein J. Org. Chem. 2012, 8, 994–1002, doi:10.3762/bjoc.8.112

• of oxidation. Whereas tetrathiafulvalenes and analogues [1][2][3][4][5] have principally found widespread applications in materials science, tetraazaalkenes and related compounds are much more reactive and are of potential or actual interest as reagents in synthesis [6][7][8][9][10][11][12][13][14

Synthesis and redox behavior of new ferrocene- π-extended- dithiafulvalenes: An approach for anticipated organic conductors

• Abdelwareth A. O. Sarhan,
• Omar F. Mohammed and
• Taeko Izumi

Beilstein J. Org. Chem. 2009, 5, No. 6, doi:10.3762/bjoc.5.6

• of the TTF unit into its radical cation and dication. After organic chemists had discovered organic metal tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) charge transfer complexes, various synthetic approaches to tetrathiafulvalenes gained wide attention, and charge-transfer from TTF to TCNQ

• tetrathiafulvalenes having a ferrocene moiety [10][11]. These findings prompted us to synthesize and investigate the electrochemical properties of symmetrical 1,1′-bis[(1,3-dithiol-2-ylidene)heteroaryl/aryl]ferrocenes substituted with heterocyclic and aromatic ring moieties separated by ferrocene moiety as the

Reduction of arenediazonium salts by tetrakis(dimethylamino)ethylene (TDAE): Efficient formation of products derived from aryl radicals

• Mohan Mahesh,
• John A. Murphy,
• Franck LeStrat and
• Hans Peter Wessel

Beilstein J. Org. Chem. 2009, 5, No. 1, doi:10.3762/bjoc.5.1

• successfully in the total synthesis [10] of aspidospermidine (15), the alkaloid of the Aspidosperma genus (Scheme 2). In line with our interests in generating aryl radicals by reduction of arenediazonium salts with tetrathiafulvalenes [5][6][7][8][9][10][11][12][13][14][15][16] 4 and dithiadiazafulvalenes [16