65689-53-4Relevant academic research and scientific papers
2,2'-Bi[benzo[b]thiophene]: An unexpected isolation of the benzo[b]thiophene dimer
Cheung, Eugene Y.,Pennington, Lewis D.,Bartberger, Michael D.,Staples, Richard J.
, p. 547 - 549 (2014)
The crystal structure of 2,2'-bi[benzo[b]thiophene], C16H 10S2, at 173K has triclinic (P1) symmetry. It is of interest with respect to its apparent mode of synthesis, as it is a by-product of a Stille cross-coupling reaction in which it was not explictly detected by spectroscopic methods. It was upon crystal structure analysis of a specimen isolated from the mother liquor that this reaction was determined to give rise to the title compound, which is a dimer arising from the starting material. Two independent half-molecules of this dimer comprise the asymmetric unit, and the full molecules are generated via inversion centers. Both molecules in the unit cell exhibit ring disorder, and they are essentially identical because of their rigidity and planarity.
Advantage of arch-shaped structure on transistor performances over linear-shaped structure in dibenzothienopyrrole semiconductors
Mu, Wenjing,Sun, Su,Zhang, Jing,Jiao, Mingyang,Wang, Wentao,Liu, Yanwei,Sun, Xiangnan,Jiang, Lang,Chen, Bozhen,Qi, Ting
, p. 78 - 86 (2018)
To understand the influence of molecular shape on the optoelectronic properties of heteroacenes, we report here the syntheses and characterizations of two linear- and two arch-shaped dibenzothienopyrrole (DBTP) derivatives, namely, N-hexyldibenzothieno[3,2-b:2′,3′-d]pyrrole (l-HDBTP), N-phenyldibenzothieno[3,2-b:2′,3′-d]pyrrole (l-PDBTP), N-hexyldibenzothieno[2,3-b:3′,2′-d]pyrrole (a-HDBTP) and N-phenyldibenzothieno[2,3-b:3′,2′-d]pyrrole (a-PDBTP). Their structure-property relationships have been systematically studied by optical absorption, cyclic voltammetry, single-crystal X-ray diffraction analyses and the single-crystal-based and thin-film-based field-effect transistors (FETs). The results demonstrate that the arch-shaped DBTP derivatives can modify their electronic structures and molecular arrangements by tuning of substituents, to obtain a better charge-transporting ability relative to the linear-shaped ones. The arch-shaped N-phenyl substituted a-PDBTP exhibits optimum molecular π-stacking arrangement and charge transport properties, with the hole mobility of 0.75 cm2V?1s?1 and 0.058 cm2V?1s?1 for the single-crystal and the thin-film OFETs, respectively. These results indicate that the arch-shaped DBTP core is a promising building block in the area of organic semiconducting materials.
Oxidative Homocoupling of Diheteroaryl- or Diarylmanganese Reagents Generated via Directed Manganation Using TMP2Mn
Haas, Diana,Hammann, Jeffrey M.,Moyeux, Alban,Cahiez, Gérard,Knochel, Paul
, p. 1515 - 1519 (2015)
We report an oxidative homocoupling of diheteroaryl or diarylmanganese reagents prepared by directed manganation using TMP2Mn·2MgCl2·4LiCl. The resulting diorganomanganese reagents can efficiently undergo an oxidative dimerization leading to the homocoupling products in good yields. Remarkably, a number of functional groups, as well as sensitive heterocycles are tolerated using this metalation-dimerization procedure.
Synthesis and properties of the anti and syn isomers of dibenzothieno[b,d]pyrrole
Qi, Ting,Guo, Yunlong,Liu, Yunqi,Xi, Hongxia,Zhang, Hengjun,Gao, Xike,Liu, Ying,Lu, Kun,Du, Chunyan,Yu, Giu,Zhu, Daoben
, p. 6227 - 6229 (2008)
A novel type of anti and syn isomers of a pentacyclic compound consisting of two thiophene rings and one pyrrole ring were efficiently synthesized from benzo[b]thiophene, and the anti isomer exhibits better charge transport and OFET properties compared with the syn isomer and its N-hexyl substitution. The Royal Society of Chemistry.
Stereoselective synthesis of monoamine reuptake inhibitor NS9544 acetate
Malmgren, Hakan,Cotton, Hanna,Frostrup, Brian,Jones, David Spencer,Loke, Marie-Louise,Peters, Dan,Schultz, Sara,Soelver, Ellen,Thomsen, Tove,Wennerberg, Johan
, p. 408 - 412 (2011)
(-)-3-(2-Benzothienyl)-8-H-8-azabicyclo[3,2,1]oct-2-ene acetate, NS9544 acetate, is a candidate drug intended to treat pain and other CNS disorders. In the synthetic route tropinone was enantioselective deprotonated with a chiral lithium amide derived from [R-(R*,R*)]-bis(α-methylbenzyl) amine hydrochloride. The formed enolate was trapped as triflate and coupled with benzo[b]thiophene-2-boronic acid under Suzuki conditions. To further enhance the enantiomeric purity crystallisation with l-(+)-tartaric acid was performed. Finally N-demethylation with trichloroethylchloroformate followed by treatment with acetic acid afforded NS9544 as the acetate salt with high enantiomeric purity.
Divergent Carbocatalytic Routes in Oxidative Coupling of Benzofused Heteroaryl Dimers: A Mechanistic Update
Casadio, David S.,Aikonen, Santeri,Lenarda, Anna,Nieger, Martin,Hu, Tao,Taubert, Stefan,Sundholm, Dage,Muuronen, Mikko,Wirtanen, Tom,Helaja, Juho
supporting information, p. 5283 - 5291 (2021/02/26)
Mildly thermal air or HNO3 oxidized activated carbons catalyse oxidative dehydrogenative couplings of benzo[b]fused heteroaryl 2,2’-dimers, e.g., 2-(benzofuran-2-yl)-1H-indole, to chiral 3,3’-coupled cyclooctatetraenes or carbazole-type migrative products under O2 atmosphere. DFT calculations show that the radical cation and the Scholl-type arenium cation mechanisms lead to different products with 2-(benzofuran-2-yl)-1H-indole, being in accord with experimental product distributions.
Iron-catalysed regioselective thienyl C–H/C–H coupling
Doba, Takahiro,Ilies, Laurean,Nakamura, Eiichi,Sato, Wataru,Shang, Rui
, p. 631 - 638 (2021/07/25)
Regioselective thienyl–thienyl coupling is arguably one of the most important transformations for organic electronic materials. A prototype of ideal organic synthesis to couple two thienyl groups by cutting two C–H bonds requires formal removal of two hydrogen atoms with an oxidant, which often limits the synthetic efficiency and versatility for oxidation-sensitive substrates (for example, donor and hole-transporting materials). Here, we found that diethyl oxalate, used together with AlMe3, acts as a two-electron acceptor in an iron-catalysed C–H activation. We describe the regioselective thienyl C–H/C–H coupling with an iron(III) catalyst, a trisphosphine ligand, AlMe3 and diethyl oxalate under mild conditions. The efficient catalytic system accelerated by ligand optimization polymerizes thiophene-containing monomers into homo- and copolymers bearing a variety of electron-donative π motifs. The findings suggest the versatility of iron catalysis for the synthesis of functional polymers, for which the potential of this ubiquitous metal has so far not been fully appreciated. [Figure not available: see fulltext.].
Pd-Catalyzed Aerobic Oxidative Coupling of Thiophenes: Synergistic Benefits of Phenanthroline Dione and a Cu Cocatalyst
Tereniak, Stephen J.,Bruns, David L.,Stahl, Shannon S.
supporting information, p. 20318 - 20323 (2020/12/01)
Substituted bithiophenes are prominent fragments in functional organic materials, and they are ideally prepared via direct oxidative C-H/C-H coupling. Here, we report a novel PdII catalyst system, employing 1,10-phenanthroline-5,6-dione (phd) as the ancillary ligand, that enables aerobic oxidative homocoupling of 2-bromothiophenes and other related heterocycles. These observations represent the first use of phd to support Pd-catalyzed aerobic oxidation. The reaction also benefits from a Cu(OAc)2 cocatalyst, and mechanistic studies show that Cu promotes C-C coupling, implicating a role for CuII different from its conventional contribution to reoxidation of the Pd catalyst.
Nickel-catalyzed and Li-mediated regiospecific C-H arylation of benzothiophenes
Canivet, Jér?me,Grousset, Léonie,Hisler, Ga?lle,Mohr, Yorck,Quadrelli, Elsje Alessandra,Roux, Yoann,Wisser, Florian M.
, p. 3155 - 3161 (2020/06/19)
A nickel-based catalytic system for the regiospecific C2-H arylation of benzothiophene has been established. NiCl2(bpy) is used as a catalyst in combination with LiHMDS as a base in dioxane. The catalytic system is applicable to a variety of functionalized benzothiophenes, as well as other heteroarenes including thiophene, benzodithiophene, benzofuran and selenophene in combination with iodo aryl electrophiles. The role of LiHMDS as a uniquely potent base and a postulated mechanism are discussed. The applicability of this system is finally demonstrated for the synthesis of an intermediate of an active pharmaceutical ingredient.
Copper- and Cobalt-Catalyzed Syntheses of Thiophene-Based Tertiary Amines
Bouarfa, Salima,Gra?l, Simon,Ivanova, Maria,Langlais, Timothy,Bentabed-Ababsa, Ghenia,Lassagne, Frédéric,Erb, William,Roisnel, Thierry,Dorcet, Vincent,Knochel, Paul,Mongin, Florence
, p. 3244 - 3258 (2019/06/08)
Thienylzinc halides and related compounds prepared by deprotonation followed by transmetalation were used in copper-catalyzed amination using N-benzoyloxy secondary amines. By extending the reaction to 1,5-naphthyridine, it was showed that the competitive dimer formation observed in the case of thiophenes was linked with the low stability of some thienylamines rather than homocoupling. Interestingly, thienylzinc halides and related compounds prepared by transmetalation of thienylmagnesium halides, either prepared from their bromo-precursors or generated by deprotometalation, were satisfactorily employed in cobalt-catalyzed aminations. Finally, aminothiophenes were involved in copper-catalyzed mono- and di-N-arylations, affording differently substituted di- and triphenylamines.
