Synthesis of aryl-substituted thieno[3,2-b]thiophene derivatives and their use for N,S-heterotetracene construction

• Nadezhda S. Demina,
• Nikita A. Kazin,
• Nikolay A. Rasputin,
• Roman A. Irgashev and
• Gennady L. Rusinov

Beilstein J. Org. Chem. 2019, 15, 2678–2683, doi:10.3762/bjoc.15.261

• -heteroacenes, which can limit the effectiveness of semiconducting films in the case of solution-processable electronics [11]. Introducing the NH-containing moieties, e.g., pyrrole rings, followed by attaching solubilizing substituents is one of the ways to solve this problem. Thus, different types of N,S

AgNTf₂-catalyzed formal [3 + 2] cycloaddition of ynamides with unprotected isoxazol-5-amines: efficient access to functionalized 5-amino-1H-pyrrole-3-carboxamide derivatives

• Ziping Cao,
• Jiekun Zhu,
• Li Liu,
• Yuanling Pang,
• Laijin Tian,
• Xuejun Sun and
• Xin Meng

Beilstein J. Org. Chem. 2019, 15, 2623–2630, doi:10.3762/bjoc.15.255

• Analysis, Qufu 273165, P. R. China 10.3762/bjoc.15.255 Abstract A formal [3 + 2] cycloaddition between ynamides and unprotected isoxazol-5-amines has been developed in the presence of catalytic AgNTf2 in an open flask. By the protocol, a variety of functionalized 5-amino-1H-pyrrole-3-carboxamide

• derivatives can be obtained in up to 99% yield. The reaction mechanism might involve the generation of an unusual α-imino silver carbene intermediate (or a silver-stabilized carbocation) and subsequent cyclization/isomerization to build the significant pyrrole-3-carboxamide motif. The reaction features the

• use of an inexpensive catalyst, simple reaction conditions, simple work-up without column chromatographic purification for most of products and high yields. Keywords: [3 + 2] cycloaddition; isoxazole; pyrrole; silver catalysis; ynamide; Introduction Silver-catalyzed transformations of alkynes have

In search of visible-light photoresponsive peptide nucleic acids (PNAs) for reversible control of DNA hybridization

• Lei Zhang,
• Greta Linden and
• Olalla Vázquez

Beilstein J. Org. Chem. 2019, 15, 2500–2508, doi:10.3762/bjoc.15.243

• cis-form did not show any decomposition under these conditions (Figure S27C, Supporting Information File 1), unlike when the oF4Azo was grafted onto a pyrrole scaffold [48]. Next, we explored if the inclusion of oF4Azo as monomer surrogate within the PNA sequence could affect its hybridization to a

Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis

• Zhen Cao,
• Aline Lacoudre,
• Cybille Rossy and
• Brigitte Bibal

Beilstein J. Org. Chem. 2019, 15, 2465–2472, doi:10.3762/bjoc.15.239

• of silver(I) complexes 1a–d, we investigated their performance in the cyclization [63] of alkynone 3 [63][64][65] in the presence of benzylamine, as a nucleophile (Table 2) that lead to substituted pyrrole 5. This tandem condensation/cycloisomerization was previously reported in 78% yield using AgOTf

• % were employed (Table 2, entries 2–6). Interestingly, a lower catalytic loading of 0.5 mol % allowed the isolation of 73% of pyrrole 5 in the presence of catalysts 1a and 1b (Table 2, entries 7 and 8). Under the same conditions, the catalytic efficiency of 1c and 1d was slightly lower (64–67 % yield

• acetate 70:1) to obtain pyrrole 5. X-ray structures of complex 1a, as two diastereoisomeric macrocycles (R,S-1)2·(AgOTf)2 with ligands assembled in: (a) a head-to-head fashion and, (b) a head-to-tail mode. Hydrogen atoms are omitted for clarity. X-ray structure of complex 1c, as a (R,S-1)4·(AgNO3)6 cage

Combining the Ugi-azide multicomponent reaction and rhodium(III)-catalyzed annulation for the synthesis of tetrazole-isoquinolone/pyridone hybrids

• Gerardo M. Ojeda,
• Prabhat Ranjan,
• Pavel Fedoseev,
• Lisandra Amable,
• Upendra K. Sharma,
• Daniel G. Rivera and
• Erik V. Van der Eycken

Beilstein J. Org. Chem. 2019, 15, 2447–2457, doi:10.3762/bjoc.15.237

• isoquinolones is very wide and may be extended to the preparation of complex compounds having heterocyclic moieties such as pyridone, furan, thiophene and pyrrole, as well as the corresponding benzo-fused derivatives. The developed procedure is simple, reproducible and does not require inert conditions

• rings, such as furan, benzofuran, pyrrole, benzopyrrole, thiophene, benzothiophene and naphthalene were also successfully synthesized (5d–l) in moderate to very good yields. The exceptions were the cases of indolopyridone 5i and thiazolopyridone 5k, the latter one could not be obtained even after many

1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• selectivity of this receptor for chloride anion is due to the cavity size (see Figure 3) [37]. 2.2. Optical anion sensing by 1,2,3-triazolium macrocycles within porphyrin cages Various porphyrin-based host supramolecules containing hydrogen-bond donor groups such as integrated amide, urea, pyrrole, ammonium

• donors: The benefits of combining the triazolium motif with other hydrogen bond donor motifs has been explored by Sessler et al. and they have synthesized a pyrrole based tetra-1,2,3-triazolium macrocycle 10 (Figure 10) via the tetraalkylation of a triazole macrocycle originally prepared via click

• chemistry. Different hydrogen bond donors such as pyrrole N–H and benzene C–H along with the triazolium C5–H have been successfully incorporated within a single macrocyclic framework. The complex formation of anions with the hydrogen bond donors varied according to the polarity of the solvent. It was found

Characterization of two new degradation products of atorvastatin calcium formed upon treatment with strong acids

• Jürgen Krauß,
• Monika Klimt,
• Markus Luber,
• Peter Mayer and
• Franz Bracher

Beilstein J. Org. Chem. 2019, 15, 2085–2091, doi:10.3762/bjoc.15.206

• /dehydration process in the side chain), treatment with conc. aqueous hydrochloric acid gave a complex, bridged molecule under C–C-bond formation of the lactone moiety with the pyrrole, migration of the isopropyl group and loss of the carboxanilide residue. The novel degradation products were characterized by

• , no signal was observed which could be attributed to a C–H group at the pyrrole ring. The 13C NMR data showed one carbonyl resonance at 170.3 ppm, assignable to a lactone moiety. The HMBC experiment showed a cross peak between the proposed lactone carbonyl carbon and a neighboring CH-O group

• anhydrous acid conditions, the entire carboxanilide residue was removed to give the (S)-configured 4-unsubstituted pyrrole 7, as exemplified by a typical CH resonance at 6.20 ppm in the 1H NMR spectrum. This structure was further confirmed by X-ray data (see Figure 2 and Supporting Information File 1). HPLC

Identification of optimal fluorescent probes for G-quadruplex nucleic acids through systematic exploration of mono- and distyryl dye libraries

• Xiao Xie,
• Michela Zuffo,
• Marie-Paule Teulade-Fichou and
• Anton Granzhan

Beilstein J. Org. Chem. 2019, 15, 1872–1889, doi:10.3762/bjoc.15.183

• analytes. Although our results do not allow to formulate comprehensive structure–properties relationships, we identified several structural motifs, such as indole- or pyrrole-substituted distyryl dyes, as well as simple mono-stryryl dyes such as DASPMI [2-(4-(dimethylamino)styryl)-1-methylpyridinium iodide

• containing pyrrole residues (1x, 7x: blue dots in Figure 6) also demonstrate outstanding fluorescence enhancement in the presence of G4-DNA analytes (1x: up to 690-fold with TERRA; 7x: up to 220-fold with c-kit2). However, in the case for 1x, a marked loss of selectivity with respect to non-G4 analytes can

• dot distribution in the plot, the mono-styryl motif and the pyrrole substituent within the distyryl motif (1x, 7x) clearly promote the selectivity for the parallel G4 structures. On the other side, the effect of the indole motif is less clear, with most of the dyes not displaying any well-defined

Functional panchromatic BODIPY dyes with near-infrared absorption: design, synthesis, characterization and use in dye-sensitized solar cells

• Quentin Huaulmé,
• Cyril Aumaitre,
• Outi Vilhelmiina Kontkanen,
• David Beljonne,
• Alexandra Sutter,
• Gilles Ulrich,
• Renaud Demadrille and
• Nicolas Leclerc

Beilstein J. Org. Chem. 2019, 15, 1758–1768, doi:10.3762/bjoc.15.169

• synthesis of the target materials is schemed in Figure 4. To introduce the selected substitution pattern, 2,3-dimethylpyrrole 1 is first synthesized through a Trofimov reaction in a one-pot two-step reaction [29]. The condensation of the aforementioned pyrrole on para-iodobenzoyl chloride affords the

A heteroditopic macrocycle as organocatalytic nanoreactor for pyrroloacridinone synthesis in water

• Piyali Sarkar,
• Sayan Sarkar and
• Pradyut Ghosh

Beilstein J. Org. Chem. 2019, 15, 1505–1514, doi:10.3762/bjoc.15.152

• apoptotic cells, the investigation of the morphology of nuclei, the direct counting of cultivable bacteria, DNA intercalators, etc. [1][2][3][4]. Pyrrole, another biologically active heterocyclic compound, when fused with acridines affords promising bioactive pyrroloacridinone moieties demonstrating

Synthesis of pyrrolo[1,2-a]quinolines by formal 1,3-dipolar cycloaddition reactions of quinolinium salts

• Anthony Choi,
• Rebecca M. Morley and
• Iain Coldham

Beilstein J. Org. Chem. 2019, 15, 1480–1484, doi:10.3762/bjoc.15.149

• with electron-poor alkenes occurs through a stepwise conjugate addition–cyclization process [23]. We were interested in the related quinolinium ylides that, on (formal) cycloaddition would provide pyrrolo[1,2-a]quinolines as products. These are tricyclic compounds consisting of a pyrrole ring fused

Introduction of an isoxazoline unit to the β-position of porphyrin via regioselective 1,3-dipolar cycloaddition reaction

• Xiujun Liu,
• Xiang Ma and
• Yaqing Feng

Beilstein J. Org. Chem. 2019, 15, 1434–1440, doi:10.3762/bjoc.15.143

• four pyrrole rings with respect to the porphyrin mean plane, which are more twisted than that in normal Zn-porphyrin [49]. The lengths of Zn–N bonds range from 2.041 Å to 2.073 Å. The new formed five-membered isoxazoline ring is almost vertical (with a dihedral angle of 82.7°) to the mean plane of the

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

• Pierre-Olivier Schwartz,
• Sebastian Förtsch,
• Astrid Vogt,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2019, 15, 1379–1393, doi:10.3762/bjoc.15.138

• of 0.49 V, is much easier to oxidize due to the electron-rich character of the pyrrole ring [47]. The HOMO energy levels were determined from the onset of the oxidation wave and accordingly gradually decreased from 1 to 4 (−5.92 eV to −5.80 eV) (Table 4, Figure 7). Due to the absence of reduction

Extending mechanochemical porphyrin synthesis to bulkier aromatics: tetramesitylporphyrin

• Qiwen Su and
• Tamara D. Hamilton

Beilstein J. Org. Chem. 2019, 15, 1149–1153, doi:10.3762/bjoc.15.111

• mechanochemical condensation with pyrrole to give meso-tetrakis[2,4,6-(trimethyl)phenyl]porphyrin (TMP) after oxidation in solution. Yields are similar to those obtained using high-temperature porphyrin synthesis, although they remain significantly lower than some optimized room-temperature, solution-based

• materials, namely: pyrrole and an aldehyde (Scheme 1). Porphyrin synthesis is interesting to study as a mechanochemical reaction because it involves the combination of reactive molecules under appropriate conditions to give a very stable, aromatic product. Furthermore, depending on the nature of the

• work on mechanochemical porphyrin synthesis has demonstrated that it is possible to synthesize tetraphenylporphyrin (TPP) by grinding benzaldehyde and pyrrole (two liquids) in the presence of an acid catalyst, followed by oxidation with DDQ in minimal amounts of solvent [19]. TPP was produced in a

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• (Scheme 4). In this case, copper catalyst and alkynes are also used but, unlike the above method, alkynes 18 are monosubstituted. The third component is an indole or pyrrole derivative 19 and the result of the reaction is a 3,3-disubstituted isoindolinone derivative 20, which contains a newly formed

• quaternary centre [79]. The reaction takes places in water, even in the presence of air, and with nanodomain cuprous oxide as an inexpensive and reusable catalyst. The scope includes aryl, alkyl and carboxyl groups at 2- and 3-positions of the lactam ring. Pyrrole reacts across the 2-carbon while indole

• similar way to that described in Scheme 3. In this case, the coupled alkyne moiety is again activated by Cu(I) and then base-promoted cyclization occurs. A new copper complex formation with the alkene analogue to 13 (see Scheme 3) facilitates the aromatic nucleophilic substitution by indole or pyrrole

Novel (2-amino-4-arylimidazolyl)propanoic acids and pyrrolo[1,2-c]imidazoles via the domino reactions of 2-amino-4-arylimidazoles with carbonyl and methylene active compounds

• Victoria V. Lipson,
• Tetiana L. Pavlovska,
• Nataliya V. Svetlichnaya,
• Anna A. Poryvai,
• Nikolay Yu. Gorobets,
• Erik V. Van der Eycken,
• Irina S. Konovalova,
• Svetlana V. Shiskina,
• Alexander V. Borisov,
• Vladimir I. Musatov and
• Alexander V. Mazepa

Beilstein J. Org. Chem. 2019, 15, 1032–1045, doi:10.3762/bjoc.15.101

• compounds of both natural and synthetic origin, containing in their structure pyrrole and imidazole rings, display a wide set of pharmacologically significant activities. The most important natural sources of such systems are marine sponges. Since the 70's of 20th century up to date more than 150

• derivatives containing pyrrole and 2-aminoimidazole fragments in their structure were found among the metabolites of these marine organisms [1]. This group of compounds is characterized by an exceptional molecular diversity. The main structural types of these substances are shown in Figure 1. The metabolites

• . are a source of alkaloids with core structures containing simultaneously pyrrole carboxamide and 2-aminoimidazole moieties such as the simple achiral compound oroidine (V) and spatially organized molecules in a complex manner with a large number of chiral centres like (−)-palau’amine (VI) [3

The LANCA three-component reaction to highly substituted β-ketoenamides – versatile intermediates for the synthesis of functionalized pyridine, pyrimidine, oxazole and quinoxaline derivatives

• Tilman Lechel,
• Roopender Kumar,
• Mrinal K. Bera,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2019, 15, 655–678, doi:10.3762/bjoc.15.61

• , who treated pivalonitrile (1) with lithiated methoxyallene 2 and isolated the expected primary addition product 3 [21]. This intermediate was subjected to different cyclization conditions (Scheme 1) and the desired pyrrole derivative 4 was produced under specific conditions employing silver nitrate as

Annulation of 1H-pyrrole-2,3-diones by thioacetamide: an approach to 5-azaisatins

• Aleksandr I. Kobelev,
• Ekaterina E. Stepanova,
• Maksim V. Dmitriev and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2019, 15, 364–370, doi:10.3762/bjoc.15.32

• approaches towards this tempting scaffold are reported in the literature. They can be divided into two groups: oxidation of pyrrolo[3,2-c]pyridines [13][15][16] and annulation of pyridine by a pyrrole-2,3-dione moiety (cyclization of 2-(4-((alkoxycarbonyl)amino)pyridin-3-yl)-2-oxoacetates [11], interaction

• of 5-azaisatoic anhydride with cyanides followed by hydrolysis [10], Scheme 1). Herein, we report a distinct synthetic approach to 5-azaisatins via annulation of pyrrole-2,3-dione by a pyridine ring based on an unprecedented interaction of 1H-pyrrole-2,3-diones with thioacetamide (Scheme 1). Results

• '-pyrroles] 3. It could be either a molecule of the spiro[thiazolo-5,2'-pyrrole] 3 or a molecule of the PBT 2. To determine the most possible one, we investigated the effect of the ratio of the reagents. When we used excessive amounts of thioacetamide (fivefold excess to PBT 2a), a significant decrease in

Mn-mediated sequential three-component domino Knoevenagel/cyclization/Michael addition/oxidative cyclization reaction towards annulated imidazo[1,2-a]pyridines

• Olga A. Storozhenko,
• Alexey A. Festa,
• Delphine R. Bella Ndoutoume,
• Alexander V. Aksenov,
• Alexey V. Varlamov and
• Leonid G. Voskressensky

Beilstein J. Org. Chem. 2018, 14, 3078–3087, doi:10.3762/bjoc.14.287

• nucleophiles was tested under selected conditions. Thus, employment of pyrrole as a nucleophile gave product 7a in 43% yield, and N-methylpyrrole facilitated desired compound 7b in 23% yield (Scheme 4). Isomeric 5-, 6- and 7-azaindoles were found to be appropriate nucleophiles too, producing the corresponding

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• , triazolo[1,2-a]indazoletrione derivatives, tetrasubstituted imidazole derivatives, aromatic/aliphatic sulfide derivatives, and N-substituted pyrrole derivatives. These catalysts were used in cellulose hydrolysis, cellobiose hydrolysis, production of fatty acid ethyl ester, the transesterification of

• derivatives. The synthetic route for MWCNT-SO3H and its catalytic application for the synthesis of N-substituted pyrrole derivatives. The sulfonic acid-functionalized polymers (P-SO3H) covalently

Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles

• Takashi Go,
• Akane Morimatsu,
• Hiroaki Wasada,
• Genzoh Tanabe,
• Osamu Muraoka,
• Yoshiharu Sawada and
• Mitsuhiro Yoshimatsu

Beilstein J. Org. Chem. 2018, 14, 2722–2729, doi:10.3762/bjoc.14.250

• (diols). Seleno-Pummerer reactions of 3-selanylmethylpyrroles also proceeded via in situ generation of selenoxides, followed by a treatment with TBAH. Keywords: hydroamination; Pummerer reaction; pyrrole; pyrroloazepine; 1,7-sulfur shift; Introduction Pyrrolo- and indoloazepine skeletons are chemical

• radical cyclisations [28] and the 1,7-electrocyclisation of azomethine ylides or ring expansion sequences [29]), most of these approaches are ineffective for synthesising pyrrolo[3,2-c]azepines. Recently, Echavarren and Beller reported a novel Au- or Pt-catalysed cycloisomerisation reaction of pyrrole-2

• determined by analysing the single-crystal X-ray diffraction spectrum of the corresponding sulfone of 4a; the structure was a pyrrole bearing both 3-sulfanylmethyl and 4-allylaminomethyl groups (see Supporting Information File 1). To develop a useful Pummerer reaction procedure, we selected allylamine

Synthesis of aryl sulfides via radical–radical cross coupling of electron-rich arenes using visible light photoredox catalysis

• Amrita Das,
• Mitasree Maity,
• Simon Malcherek,
• Burkhard König and
• Julia Rehbein

Beilstein J. Org. Chem. 2018, 14, 2520–2528, doi:10.3762/bjoc.14.228

• -methoxyphenyl) disulfide was employed as the thiolating agent (3h). With symmetrical arenes, diarylation was observed. The initially formed mono-arylated product is more reactive than the starting material and reacts to the diarylthiol product. When 1-phenyl-1H-pyrrole-2,5-dione was employed as the arene, the

Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies

• Paris E. Georghiou,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Hidetaka Nishimura,
• Jaehyun Lee,
• Atsushi Wakamiya and
• Lawrence T. Scott

Beilstein J. Org. Chem. 2018, 14, 2488–2494, doi:10.3762/bjoc.14.225

• reported in the literature [7]. Besides the classical calixarene phenolic subunits linked by methylene groups, “calixarenes” incorporating other subunits include, but are not limited to, resorcinol [8], hydroquinone [9], naphthols [10], pyrrole [11], heteroaromatics [12] and triptycene [13] in their cavity

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• in the presence of CoCp*(CO)I2 and AgNTf2 (Scheme 38) [98]. The reaction tolerated various pyrimidine containing arenes, such as indole, phenyl, and pyrrole with different ketenimines to form enaminylation products 61. Subsequently, the hydroarylation products 61 were further converted into bioactive

Investigation of the electrophilic reactivity of the biologically active marine sesquiterpenoid onchidal and model compounds

• Melissa M. Cadelis and
• Brent R. Copp

Beilstein J. Org. Chem. 2018, 14, 2229–2235, doi:10.3762/bjoc.14.197

• aminated pyrrole adducts. Somewhat surprisingly, no reaction was observed between onchidal and n-pentanethiol. Structurally simplified n-pentyl 11–13 and cyclohexylmethyl 15–17 analogues of onchidal were prepared and demonstrated similar amine-selective reactivity. Onchidal and analogues reacted with the

• model protein lysozyme, forming covalent adducts and leading to protein cross-linking. These results provide preliminary evidence supporting the molecular mechanism of biological activity exhibited by onchidal. Keywords: dialdehyde; lysozyme; mollusc; onchidal; pyrrole; Introduction More than 80

• binneyi) also exhibit biological properties including feeding deterrence, antibacterial and anticholinesterase activities. Chemical reactivity studies using polygodial (1), scalaradial (2) and caulerpenyne (3) have demonstrated evidence of pyrrole formation upon reaction with primary amines, with