An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

Fluorogenic PNA probes

• Tirayut Vilaivan

Beilstein J. Org. Chem. 2018, 14, 253–281, doi:10.3762/bjoc.14.17

• background and good response with DNA, as well as offering an excellent specificity [65]. In addition to fluorophore-quencher interactions, FRET [66] and pyrene monomer–excimer switching [67][68] have been employed as alternative mechanisms for inducing fluorescence changes in the DNA probes. The FRET and

• monomer–excimer switching beacons are also fluorescent in the unbound state, and therefore it is possible to monitor the success of cellular delivery. In the case of pyrene monomer–excimer switching, the long fluorescence lifetime of the pyrene excimers allows facile elimination of background signals from

• autofluorescence by time-resolved fluorescence measurements. A few monomer–excimer switching PNA probes have been reported. Two or more pyrene labels may be conveniently placed anywhere in the PNA molecule by attaching them to a C5-functionalized thymine via amide or click chemistries, and applications for the

Recent applications of click chemistry for the functionalization of gold nanoparticles and their conversion to glyco-gold nanoparticles

• Vivek Poonthiyil,
• Thisbe K. Lindhorst,
• Vladimir B. Golovko and
• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 11–24, doi:10.3762/bjoc.14.2

• substitution by reaction with NaN3 then resulted in AuNPs with mixed monolayers containing 52% N3- and 44% CH3-terminated alkanethiol ligands. A series of alkynes were synthesised, including derivatives of nitrobenzene (1), ferrocene (2), anthracene (3), pyrene (4), aniline (5), and polyethylene glycol (6) all

Synthesis of 1,3-cis-disubstituted sterically encumbered imidazolidinone organocatalysts

• Jan Wallbaum and
• Daniel B. Werz

Beilstein J. Org. Chem. 2017, 13, 2577–2583, doi:10.3762/bjoc.13.254

• starting from easily accessible substrates. Different natural and unnatural amino acid methyl amides were cyclized with aromatic carbaldehydes to yield two diastereomeric MacMillan-type catalysts. Special emphasis was put on bulky residues such as mesityl and pyrene moieties. Keywords: imidazolidinone

• transformation (shown in Scheme 1b) delivered relatively high selectivity with imidazolidinones derived from L-phenylalanine this amino acid derivative was used as coupling partner. 1-Pyrene carbaldehyde 10b gave only a minor excess of the cis-diastereomer (S,S)-3b. For mesityl carbaldehyde 10c the desired

• , 1.0 equiv), pyrene-1-carbaldehyde (1.73g, 7.50 mmol, 1.5 equiv), 4 Å molecular sieves (400 mg) and Yb(OTf)3 (310 mg, 500 µmol, 10 mol %) in THF (20 mL) were reacted according to the GP. Silica gel column chromatography (n-pentane/EtOAc 4:1 → 2:1 → 1:2) gave the faster eluting (R,S)-diastereomer (R,S

Pyrene–nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies

• Artur Jabłoński,
• Yannic Fritz,
• Hans-Achim Wagenknecht,
• Rafał Czerwieniec,
• Tytus Bernaś,
• Damian Trzybiński,
• Krzysztof Woźniak and
• Konrad Kowalski

Beilstein J. Org. Chem. 2017, 13, 2521–2534, doi:10.3762/bjoc.13.249

• Chemistry, Biological and Chemical Research Centre, University of Warsaw, Żwirki and Wigury 101, 02-089 Warszawa, Poland 10.3762/bjoc.13.249 Abstract Fluorescent pyrene–linker–nucleobase (nucleobase = thymine, adenine) conjugates with carbonyl and hydroxy functionalities in the linker were synthesized and

• characterized. X-ray single-crystal structure analysis performed for the pyrene–C(O)CH2CH2–thymine (2) conjugate reveals dimers of molecules 2 stabilized by hydrogen bonds between the thymine moieties. The photochemical characterization showed structure-dependent fluorescence properties of the investigated

• compounds. The conjugates bearing a carbonyl function represent weak emitters as compared to compounds with a hydroxy function in the linker. The self-assembly properties of pyrene nucleobases were investigated in respect to their binding to single and double strand oligonucleotides in water and in buffer

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

Beilstein J. Org. Chem. 2017, 13, 1828–1849, doi:10.3762/bjoc.13.178

• were isolated in quantitative yields. The amination reaction was then performed on a number of substrates, ranging from simple mono- and disubstituted anilines, benzylamines and polyaromatic amines such as anthracene-, phenanthrene-, pyrene- and crysenamine (Scheme 12). An interesting feature of LAG

Regioselective (thio)carbamoylation of 2,7-di-tert-butylpyrene at the 1-position with iso(thio)cyanates

• Anna Wrona-Piotrowicz,
• Marzena Witalewska,
• Janusz Zakrzewski and
• Anna Makal

Beilstein J. Org. Chem. 2017, 13, 1032–1038, doi:10.3762/bjoc.13.102

• ; pyrene; thioamide; Introduction Direct functionalization of pyrene 1 has attracted a great deal of attention in recent years because it is the most straightforward route to novel organic molecular materials for optoelectronic devices (OLEDs, field-effect transistors, fluorescent sensors, dye lasers, etc

• reported an efficient method for the synthesis of pyrene-1-carbothioamides via reaction of pyrene with isothiocyanates in the presence of trifluoromethanesulfonic (triflic) acid (TfOH) [11][12]. Since 2 was used as a starting material in the syntheses of various pyrenyl fluorophores exhibiting unique

• , for the reaction with p-methoxyphenyl isothiocyanate we were able to obtain, by crystallization, the major product, C(1)-substituted thioamide 3n, contaminated with only ≈5% of its C4-substituted counterpart. We tentatively explain this poorer regioselectivity by possible π–π interaction of pyrene

A new class of organogelators based on triphenylmethyl derivatives of primary alcohols: hydrophobic interactions alone can mediate gelation

• Wangkhem P. Singh and
• Rajkumar S. Singh

Beilstein J. Org. Chem. 2017, 13, 138–149, doi:10.3762/bjoc.13.17

• ][24]. Similar is the case for π-stacking interaction (seen in naphthalene, anthracene, pyrene, perylene, etc.) which has been mostly used in combination with other types of secondary interactions in the discovery of many gelators [25][26]. This holds true for many other non-covalent interactions as

• geometry (unlike the planar geometry of say anthracene, pyrene, etc.), π–π stacking will be favoured only between benzene units of different trityl groups. A small library of triphenylmethyl derivatives was synthesized from the corresponding primary alcohols employing a single step reaction and detailed

Benzothiadiazole oligoene fatty acids: fluorescent dyes with large Stokes shifts

• Lukas J. Patalag and
• Daniel B. Werz

Beilstein J. Org. Chem. 2016, 12, 2739–2747, doi:10.3762/bjoc.12.270

• methods are commonly employed. Either unnatural fluorescent dyes are inserted into the membrane (e.g., pyrene) or the hydrophilic part of lipids is utilized for the covalent attachment of fluorophores. Another possibility is the use of fluorescently labelled antibodies which bind membrane components such

• -dipyrromethene) [11][12], BOIMPY- (bis(borondifluoride)-8-imidazodipyrromethene) [13] and pyrene-labeled fatty acids [14]. Of course, all these alterations might also affect the membrane structure and its dynamics. While the NBD-fluorophore suffers from unsuitable polarity, a pyrene motif disrupts the unpolar

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

• Élise Euvrard,
• Nadia Morin-Crini,
• Coline Druart,
• Justine Bugnet,
• Bernard Martel,
• Cesare Cosentino,
• Virginie Moutarlier and
• Grégorio Crini

Beilstein J. Org. Chem. 2016, 12, 1826–1838, doi:10.3762/bjoc.12.172

• PAHs: naphthalene (NAP), acenaphthene (ACE), acenaphthylene (ACY), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FLT) and pyrene (PYR); eight heavy PAHs: benz[a]anthracene (BaANT), chrysene (CHY), benzo[b]fluoranthene (BbFLT), benzo[k]fluoranthene (BkFLT), benzo[a]pyrene (BaPYR

• ), dibenz[a,h]anthracene (dBahANT), indeno[1,2,3-cd]pyrene (IcdPYR) and benzo[g,h,i]perylene (BghiPL); three APs: 4-nonylphenol (4NP, CAS no. 84852-15-3), 4-n-nonylphenol (4nNP, CAS no. 104-40-5) and 4-tert-octylphenol (4tOP, CAS no. 140-66-9). Calcium chloride and sodium bicarbonate were purchased from

Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells

• Hideaki Komiyama,
• Chihaya Adachi and
• Takuma Yasuda

Beilstein J. Org. Chem. 2016, 12, 1459–1466, doi:10.3762/bjoc.12.142

• their extended dimensionality, in comparison to their linear analogues. Star-shaped π-conjugated molecules consisting of hexa-peri-hexabenzocoronene [8][9][10][11][12][13][14], pyrene [15][16][17], and triphenylamine [18][19][20][21][22][23] central cores have been developed as donor materials for BHJ

Application of Cu(I)-catalyzed azide–alkyne cycloaddition for the design and synthesis of sequence specific probes targeting double-stranded DNA

• Svetlana V. Vasilyeva,
• Vyacheslav V. Filichev and
• Alexandre S. Boutorine

Beilstein J. Org. Chem. 2016, 12, 1348–1360, doi:10.3762/bjoc.12.128

• ][13][14][15]. Recently a new class of TFOs containing covalently linked intercalating pyrene moieties, so-called "twisted intercalating nucleic acids" (TINA), has been described [16][17]. TINA-TFOs form stable and specific triplexes with target dsDNA at physiological conditions. It has been shown that

• ). Purification of TINA oligonucleotides by reversed phase HPLC was quite difficult. Due to the high hydrophobicity of the pyrene moiety the retention time of the parent oligonucleotide and the conjugate were very close to each other and their peaks were overlapped. Thus preparative denaturing gel electrophoresis

Synthesis, fluorescence properties and the promising cytotoxicity of pyrene–derived aminophosphonates

• Jarosław Lewkowski,
• Maria Rodriguez Moya,
• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Renata Kontek and
• Gabriela Gajek

Beilstein J. Org. Chem. 2016, 12, 1229–1235, doi:10.3762/bjoc.12.117

• normal lymphocytes (IC50 = 230.8 µM). Keywords: aminophosphonic derivatives; cytotoxicity; fluorescence properties; MTT test; pyrene-1-carboxaldehyde; Introduction The biological activity of aminophosphonic systems is very well known and described, in aspect of their crop protective [1], antibacterial

• [2] or anticancer properties [3]. Various C-aryl substituted derivatives of phosphonoglycine have been synthesized including those of benzene and several polycyclic aromatic hydrocarbons [4], five- [5] and six-membered [6] heteroaromatic compounds and even ferrocene [7]. In contrast, pyrene-based

• derivatives, e.g., amino(pyrene-1-yl)methyl phosphonic acid derivatives have been described only twice in the chemical literature. Firstly, Harry Hudson’s team [8] published the synthesis of diethyl N-benzhydrylamino(pyrene-1-yl)methylphosphonate in a series of N-benzhydryl substituted aminomethyl

Stimuli-responsive HBPS-g-PDMAEMA and its application as nanocarrier in loading hydrophobic molecules

• Yongsheng Chen,
• Li Wang,
• Haojie Yu,
• Zain-Ul-Abdin,
• Ruoli Sun,
• Guanghui Jing,
• Rongbai Tong and
• Zheng Deng

Beilstein J. Org. Chem. 2016, 12, 939–949, doi:10.3762/bjoc.12.92

• results showed that size of aggregates was affected by a corresponding stimulus. In addition, the loading ability of HBPS-g-PDMAEMA aggregates was investigated by using pyrene or Nile red as the model guest molecules by using UV–vis and fluorescence spectroscopy. The results showed that HBPS-g-PDMAEMA

• distribution which means that these stimuli-responsive polymers may be suitable for medicinal use. The encapsulation of hydrophobic molecules in HBPS-g-PDMAEMA aggregates To confirm the loading capability of HBPS-g-PDMAEMA aggregates for hydrophobic molecules, pyrene was used as a model molecule. Pyrene, a

• fluorescence-sensitive molecule, is often used for detecting the local polarity of amphiphiles. To prepare the pyrene/HBPS-g-PDMAEMA aqueous sample solutions, 5 to 6 mg pyrene was added in 5 mL HBPS-g-PDMAEMA solution with concentrations from 0 to 10.0 mg/mL followed by agitation for 2 h and filtration through

Copper-mediated arylation with arylboronic acids: Facile and modular synthesis of triarylmethanes

• H. Surya Prakash Rao and
• A. Veera Bhadra Rao

Beilstein J. Org. Chem. 2016, 12, 496–504, doi:10.3762/bjoc.12.49

• respective pyrene-containing unsymmetrical triarylmethanes 11q–r in good yields (Table 3). Next, the coupling reaction of phenyl(ferrocenyl)methanol (9d) with thiophen-3-ylboronic acid (10m) provided triarylmethane 11s, which has ferrocene, thiophene and phenyl rings installed on the central carbon. The

Self and directed assembly: people and molecules

• Tony D. James

Beilstein J. Org. Chem. 2016, 12, 391–405, doi:10.3762/bjoc.12.42

• electron transfer (PET) cation sensors developed by A. P. De Silva. (b) Fluorescence photoinduced electron transfer (PET) saccharide sensor. (c) Fluorescence AND logic sensors for D-glucosamine hydrochloride. (a) Pyrene diboronic acids (n = 3–8). (b) Pyrene monoboronic acid. (c) Block chart showing the

• relative stability Krel of saccharide complexes. Obtained from the observed stability constants (Kobs) for D-glucose, D-galactose, D-fructose and D-mannose with pyrene diboronic acids (n = 3–8) divided by the observed stability constants (Kobs) with pyrene monoboronic acid, to yield relative values with

A journey in bioinspired supramolecular chemistry: from molecular tweezers to small molecules that target myotonic dystrophy

• Steven C. Zimmerman

Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14

• water-soluble tweezers (19 and 20), and pyrene tweezer 21 studied by Colquhoun. Macrocyclic diacridines and dinaphthalene and the intercalation complexes they may form with one chain in each groove. (a) Hairpin structure of CUGexp seen in (CUG)12. (b) U–U or T–T mismatches with no inter-strand hydrogen

Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

• Zhan-Jiang Zheng,
• Ding Wang,
• Zheng Xu and
• Li-Wen Xu

Beilstein J. Org. Chem. 2015, 11, 2557–2576, doi:10.3762/bjoc.11.276

• [4]arenes are sulfur-bridged analogs of calix[4]arenes, which have potential application in the molecular recognition of cationic, anionic or neutral molecules. In this regard, Yamato et al. incorporated two urea moieties possessing various aryl groups and two pyrene-appended triazole rings at the

• opposite side of the thiacalix[4]arene cavity [38]. The authors found that receptor 52 (Scheme 18) could selectively bind Cl− through hydrogen bonding interaction with the urea NH protons, and 52 can also bind with Ag+ through complexation with the pyrene-appended bistriazole. In homogeneous catalysis

• bistriazoles. The pyrene-appended thiacalix[4]arene-based bistriazole. The synthesis of triazole-based tetradentate ligands. The synthesis of phenanthroline-2,9-bistriazoles. The three-component reaction for the synthesis of bistriazoles. The one-pot synthesis of bistriazoles. The synthesis of polymer-bearing

Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid

• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Anna Gajda,
• Tadeusz Gajda,
• Anna Makal,
• Arnaud Brosseau and
• Rémi Métivier

Beilstein J. Org. Chem. 2015, 11, 2451–2458, doi:10.3762/bjoc.11.266

• , Stefana Żeromskiego116, 90-924 Łódź, Poland University of Warsaw, Biological and Chemical Research Center, Żwirki i Wigury 101, 02-089 Warszawa, Poland PPSM, ENS Cachan, CNRS, UniverSud, 61 av President Wilson, 94230 Cachan, France 10.3762/bjoc.11.266 Abstract Friedel–Crafts-type reaction of pyrene with

• diethyl 1-(isothiocyanato)alkylphosphonates promoted by trifluoromethanosulfonic acid afforded diethyl 1-(pyrene-1-carbothioamido)alkylphosphonates in 83–94% yield. These compounds were transformed, in 87–94% yield, into the corresponding diethyl 1-(pyrene-1-carboxamido)alkylphosphonates by treatment with

• Oxone®. 1-(Pyrene-1-carboxamido)methylphosphonic acid was obtained in a 87% yield by treating the corresponding diethyl phosphonate with Me3Si-Br in methanol. All of the synthesized amidophosphonates were emissive in solution and in the solid state. The presence of a phosphonato group brought about an

Molecular-oxygen-promoted Cu-catalyzed oxidative direct amidation of nonactivated carboxylic acids with azoles

• Wen Ding,
• Shaoyu Mai and
• Qiuling Song

Beilstein J. Org. Chem. 2015, 11, 2158–2165, doi:10.3762/bjoc.11.233

• reaction has a broad substrate scope. Electron-donating (4–9, 13, and 15–17) and electron-withdrawing groups (10–12, 14, 18, and 19) are also compatible in this reaction. Meanwhile, other aromatic acids such as 2-naphthylcarboxylic acid and pyrene-4-carboxylic acid also worked well under the reaction

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

• . Thus, I prepared compound 9, which bore a pyrene unit [17] (Scheme 4), based on previously published research by Sijbesma and co-workers, who had taken advantage of the excimer signal of the pyrene dimer to evaluate the stability of their famous quadruple hydrogen bonded 2-ureido-4[1H]-pyrimidinone

Design, synthesis and photochemical properties of the first examples of iminosugar clusters based on fluorescent cores

• Mathieu L. Lepage,
• Antoine Mirloup,
• Manon Ripoll,
• Fabien Stauffert,
• Anne Bodlenner,
• Raymond Ziessel and
• Philippe Compain

Beilstein J. Org. Chem. 2015, 11, 659–667, doi:10.3762/bjoc.11.74

• Strasbourg, France Institut Universitaire de France, 103 Bd Saint-Michel, 75005 Paris, France 10.3762/bjoc.11.74 Abstract The synthesis and photophysical properties of the first examples of iminosugar clusters based on a BODIPY or a pyrene core are reported. The tri- and tetravalent systems designed as

• ; fluorescent probes; iminosugars; 4-methylumbelliferone; multivalency; pyrene; Introduction Since the isolation in the 1970’s of 1-deoxynojirimycin (DNJ) from natural sources and the finding of its biological activity as an α-glucosidase inhibitor, thousands of sugar mimetics with a nitrogen atom replacing

• insights into the multivalent effect observed in CFTR correcting activity. The originality of our approach relies on the fact that, in the structures designed, this is the scaffold itself [29][30], based on a pyrene or a boron-dipyrromethene (F-BODIPY) dye, which has fluorescence activity. Results and

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

• Martin Weiser,
• Sergej Hermann,
• Alexander Penner and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

• ) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photoredox catalysts. The regioselectivity was controlled by the photocatalyst. For the

• different electron density. Representative mesoflow reactor experiments allowed to significantly shorten the irradiation times and to use sunlight as “green” light source. Keywords: electron transfer; perylene bisimide; photocatalysis; photochemistry; pyrene; Introduction Photocatalysts are organic or

• -Markovnikov-type addition of cyanide to styrene [18]. Recently, we showed by a library of different chromophores that 1-(N,N-dimethylamino)pyrene (Py) can be applied as photocatalyst for the nucleophilic addition of methanol to styrene derivatives into the Markovnikov orientation [19]. Most recently, Nicewicz

Articulated rods – a novel class of molecular rods based on oligospiroketals (OSK)

• Pablo Wessig,
• Roswitha Merkel and
• Peter Müller

Beilstein J. Org. Chem. 2015, 11, 74–84, doi:10.3762/bjoc.11.11

• functionalizations in terminal positions. First applications were presented with pyrene, cinnamoyl and anthracenyl labelled ARs. Keywords: articulated rods; click chemistry; molecular rods; oligospiroketals; pyrene excimer; Introduction One of the basic principles in living nature is based on shape-persistent and

• that articulated rods can be irreversibly fixed in the folded conformation we investigated the equilibrium between the straight and the folded shape of the articulated rods (cf. Figure 2). For this purpose we first chose pyrene moieties which are perfectly suited to detect this equilibrium owing to the

• [4 + 4] photocycloaddition of anthracene derivatives. At first we pursued a sequential approach by introducing the pyrene-1-ylacetyl and the cinnamoyl moieties in a two-step sequence in 4-hydroxypiperidine with subsequent oxidation to give piperidin-4-ones 27a,b. An appropriate anthracene derivative