DNA display of glycoconjugates to emulate oligomeric interactions of glycans

• Alexandre Novoa and
• Nicolas Winssinger

Beilstein J. Org. Chem. 2015, 11, 707–719, doi:10.3762/bjoc.11.81

• surface glycans are important actors in cellular recognition and have been implicated in numerous events such as fertilization, embryonic development, lymphocyte trafficking and cancer metastasis [1][2][3][4]. In contrast to many small molecule ligands where a functional output is often the product of a

• used to display glycans with a synergy between the interactions of the individual ligands binding with a target. Progress in this area has paralleled similar developments with small molecule conjugates [48][54][55][56][57][58][59][60][61][62][63]. Technological developments in conjugation chemistry and

Synthesis and biological evaluation of a novel MUC1 glycopeptide conjugate vaccine candidate comprising a 4’-deoxy-4’-fluoro-Thomsen–Friedenreich epitope

• Manuel Johannes,
• Maximilian Reindl,
• Bastian Gerlitzki,
• Edgar Schmitt and
• Anja Hoffmann-Röder

Beilstein J. Org. Chem. 2015, 11, 155–161, doi:10.3762/bjoc.11.15

• , the search for novel anticancer therapies is of high current interest. For instance, promising approaches such as targeted therapy with small molecule tyrosine kinase inhibitors [1][2] and active cancer immune therapy have emerged [3][4] with the latter one being particularly attractive in terms of

Organic chemistry on surfaces: Direct cyclopropanation by dihalocarbene addition to vinyl terminated self-assembled monolayers (SAMs)

• Malgorzata Adamkiewicz,
• David O’Hagan and
• Georg Hähner

Beilstein J. Org. Chem. 2014, 10, 2897–2902, doi:10.3762/bjoc.10.307

• -difluorocyclopropane-terminated SAMs by generating difluorocarbene, following the procedure of Wang et al. [22] for small molecule transformations. This involved stirring a solution of NaI (0.2 equiv) and TMSCF3 in THF (2 mL), and then immersing the silicon wafers (1 cm × 1.5 cm) into the reaction mixture at 65 °C for

Synthesis and properties of novel star-shaped oligofluorene conjugated systems with BODIPY cores

• Clara Orofino-Pena,
• Diego Cortizo-Lacalle,
• Joseph Cameron,
• Muhammad T. Sajjad,
• Pavlos P. Manousiadis,
• Neil J. Findlay,
• Alexander L. Kanibolotsky,
• Dimali Amarasinghe,
• Peter J. Skabara,
• Tell Tuttle,
• Graham A. Turnbull and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2704–2714, doi:10.3762/bjoc.10.285

• have found numerous applications as laser dyes [5][6][7], labels for biological imaging [8][9][10] and low band-gap polymers [11][12][13]. Being efficient emitters in solution, small molecule BODIPY compounds often show signs of aggregation at high concentration and in solid films [14][15], which

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• -diaza-s-indacene (BODIPY) units attached by thiophene rings have been synthesised having high molar extinction coefficients. These triads were characterised and used as donor materials in small molecule, solution processable organic solar cells. Both triads were blended with PC71BM as an acceptor in

• processing during device fabrication. The difference in power conversion efficiencies (PCEs) between polymer and small-molecule based OPVs is decreasing and PCEs over 7% have been realised in the case of the latter [18][19]. Small molecules used in OPVs are most commonly based on oligothiophenes and their

• results [26][27][28]. A PCE greater than 4% was achieved in combination with phenyl-C71-butyric acid methyl ester (PC71BM) [29]. Interestingly, a small molecule based on a DPP core substituted with electron-withdrawing units was also used as an acceptor in OPVs as a substitute for fullerene with PCEs of 1

A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

• Stefanie Wolfram,
• Hendryk Würfel,
• Stefanie H. Habenicht,
• Christine Lembke,
• Phillipp Richter,
• Eckhard Birckner,
• Rainer Beckert and
• Georg Pohnert

Beilstein J. Org. Chem. 2014, 10, 2470–2479, doi:10.3762/bjoc.10.258

• electrospray ionization MS runs by monitoring for its characteristic isotope signature. We demonstrate the universal utility of the reporter for the detection of an alkyne-modified small molecule by LC–MS and for the visualization of a model protein by in-gel fluorescence. The novel probe advantageously

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

• recognition; circular dichroism; DBTAA-adenine conjugate; ds-DNA/RNA; minor groove binding; nucleic acids; Introduction The majority of natural and artificial applications involving small molecule-DNA/RNA recognition depend on several non-covalent binding modes. Typical examples are double-stranded (ds) DNA

• /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

• advantage of nucleobase incorporation in small molecule structures for the recognition of complementary nucleotides/polynucleotides [8][9][10]. Recent studies of the novel DBTAA-adenine conjugates AP3 and AP6 (Scheme 1) showed a highly selective binding of only AP3 to poly dT among all other ss-DNA/RNA, as

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

• have excellent catalytic activities and enantioselectivities, only a few acyclic phosphines were effective. In this context, inspired by polyfunctional chiral small-molecule catalysts, particularly amino acid and thiourea-based systems [31][32], multifunctional chiral phosphines were constructed by

Organophosphorus chemistry

• Paul R. Hanson

Beilstein J. Org. Chem. 2014, 10, 2087–2088, doi:10.3762/bjoc.10.217

• number of important fields. Among the more prominent features that elevate their status as a unique and versatile class of compounds, include variable oxidation states, multivalency, asymmetry and metal-binding properties. Their presence in bioactive natural products, endogenous biomolecules, small

• molecule therapeutic agents and pro-drugs substantiates their role in modern synthetic chemistry and chemical biology. Moreover, their central use as ligands and effectors in asymmetric catalysis, as well as key functional groups for the development of new synthetic methods, has taken the field to new

Supercritical carbon dioxide: a solvent like no other

• Jocelyn Peach and
• Julian Eastoe

Beilstein J. Org. Chem. 2014, 10, 1878–1895, doi:10.3762/bjoc.10.196

• small molecule surfactants have reapplied during the design of CO2-philic polymers. The structures of polymers discussed in this review can be seen in Table 2. Fluorinated polymers: One of the first polymers reported to be solubilised in CO2 was Krytox 16350 (Table 2, compound 16), a perfluoropolyether

Multicomponent reactions in nucleoside chemistry

• Mariola Koszytkowska-Stawińska and
• Włodzimierz Buchowicz

Beilstein J. Org. Chem. 2014, 10, 1706–1732, doi:10.3762/bjoc.10.179

• ) represent an excellent tool for the generation of libraries of small-molecule compounds, for instance they are indispensable for the structure–activity relationship (SAR) studies. Many excellent comprehensive reviews on MCRs have been published. The reviews have covered the significant topics in this field

Aryl substitution of pentacenes

• Andreas R. Waterloo,
• Anna-Chiara Sale,
• Dan Lehnherr,
• Frank Hampel and
• Rik R. Tykwinski

Beilstein J. Org. Chem. 2014, 10, 1692–1705, doi:10.3762/bjoc.10.178

• ], and specifically 6,13-(triisopropylsilylethynyl)pentacene (TIPSPc) [13][14]. The latter was synthesized by Anthony over a decade ago [16], but it is still a leading focus of the scientific community. Substituted pentacenes can offer several advantages to other small molecule semiconductors, including

An experimental and theoretical NMR study of NH-benzimidazoles in solution and in the solid state: proton transfer and tautomerism

• Carla I. Nieto,
• Pilar Cabildo,
• M. Ángeles García,
• Rosa M. Claramunt,
• Ibon Alkorta and
• José Elguero

Beilstein J. Org. Chem. 2014, 10, 1620–1629, doi:10.3762/bjoc.10.168

• heterocycles it can be said that they have relevant biological and medicinal chemistry properties, because, for instance, over 80% of top small molecule drugs by US retail sales in 2010 contain at least one heterocyclic fragment in their structures [1]. Benzimidazoles besides being the skeleton of many

Syntheses of fluorooxindole and 2-fluoro-2-arylacetic acid derivatives from diethyl 2-fluoromalonate ester

• Antal Harsanyi,
• Graham Sandford,
• Dmitri S. Yufit and
• Judith A.K. Howard

Beilstein J. Org. Chem. 2014, 10, 1213–1219, doi:10.3762/bjoc.10.119

• –fluorine bonds are ‘man-made’. Syntheses rely either on the construction of carbon–fluorine bonds using a fluorinating agent (‘late-stage’ fluorination) or the application of polyfunctional fluorine-containing small molecule building blocks (‘early stage’ fluorination) which may be employed in further

Automated solid-phase peptide synthesis to obtain therapeutic peptides

• Veronika Mäde,
• Sylvia Els-Heindl and
• Annette G. Beck-Sickinger

Beilstein J. Org. Chem. 2014, 10, 1197–1212, doi:10.3762/bjoc.10.118

• interesting target on the pharmaceutical market. In terms of molecular weight, peptides bridge the gap between small molecule drugs (<500 Da) and protein-based pharmaceuticals (>5,000 Da) and enable a possible medication of incurable pathologies [3]. Diseases such as cancer, diabetes, obesity but also

Rapid pseudo five-component synthesis of intensively blue luminescent 2,5-di(hetero)arylfurans via a Sonogashira–Glaser cyclization sequence

• Fabian Klukas,
• Alexander Grunwald,
• Franziska Menschel and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 672–679, doi:10.3762/bjoc.10.60

• structurally related to small molecule inhibitors of p53-HDM-2 [21][22][23]. Electronic properties and computational studies All title compounds 2 display strong fluorescence in solution and in the solid state upon UV excitation (Figure 1). Therefore, the absorption and emission spectra of all compounds 2 were

Integration of enabling methods for the automated flow preparation of piperazine-2-carboxamide

• Richard J. Ingham,
• Claudio Battilocchio,
• Joel M. Hawkins and
• Steven V. Ley

Beilstein J. Org. Chem. 2014, 10, 641–652, doi:10.3762/bjoc.10.56

• pyrazine 2 to piperazine 1 (Figure 2b). Both of these steps involve flowing through heterogeneous catalysts, a metal oxide for the hydration of the nitrile and a supported precious metal for the hydrogenation of the heteroaromatic ring. Furthermore, both steps involve the addition of a volatile small

• molecule to the substrate with no byproducts: the addition of water for the nitrile hydration, and the addition of hydrogen to the heteroarene for the reduction. Thus, this sequence is ideal for a fully continuous multi-step process. Results and Discussion Nitrile hydration Primary amides can be prepared

The Flögel-three-component reaction with dicarboxylic acids – an approach to bis(β-alkoxy-β-ketoenamides) for the synthesis of complex pyridine and pyrimidine derivatives

• Mrinal K. Bera,
• Moisés Domínguez,
• Paul Hommes and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2014, 10, 394–404, doi:10.3762/bjoc.10.37

• powerful tools for the assembly of small-molecule libraries [1][2]. MCRs leading to functionalized N-heterocycles [3][4][5][6][7] have long been known before the general concept of MCRs was introduced, e.g. the Hantzsch dihydropyridine synthesis [8] or the Biginelli reaction [9] leading to

Physalin H from Solanum nigrum as an Hh signaling inhibitor blocks GLI1–DNA-complex formation

• Midori A. Arai,
• Kyoko Uchida,
• Samir K. Sadhu,
• Firoj Ahmed and
• Masami Ishibashi

Beilstein J. Org. Chem. 2014, 10, 134–140, doi:10.3762/bjoc.10.10

• ) Disruption of the GLI1–DNA complex in the final stage of this signaling pathway is one of the most attractive molecular mechanisms of Hh inhibitors. Recently, we reported the first small molecule, which directly inhibits the GLI1–DNA complex formation [22].GANT61, a synthetic compound, has been reported to

Modulating NHC catalysis with fluorine

• Yannick P. Rey and
• Ryan Gilmour

Beilstein J. Org. Chem. 2013, 9, 2812–2820, doi:10.3762/bjoc.9.316

• , Münster, Germany 10.3762/bjoc.9.316 Abstract Fluorination often confers a range of advantages in modulating the conformation and reactivity of small molecule organocatalysts. By strategically introducing fluorine substituents, as part of a β-fluoroamine motif, in a triazolium pre-catalyst, it was

• :13.0). Keywords: catalysis; enantioselectivity; fluorine; gauche effect; organo-fluorine; Steglich rearrangement; Introduction Molecular editing using fluorine is a powerful strategy to modulate the conformation and reactivity of small molecule organocatalysts [1][2][3]. The negligible steric penalty

The regulation and biosynthesis of antimycins

• Ryan F. Seipke and
• Matthew I. Hutchings

Beilstein J. Org. Chem. 2013, 9, 2556–2563, doi:10.3762/bjoc.9.290

• chemotherapeutic agents whose mode of action is to trigger apoptosis. A small molecule screen identified antimycins as potent inhibitors of Bcl-2-related proteins where they were shown to bind to the hydrophobic groove [28]. A synthetic derivative of antimycin A3, 2-methoxyantimycin A3 (Figure 1), no longer

Triol-promoted activation of C–F bonds: Amination of benzylic fluorides under highly concentrated conditions mediated by 1,1,1-tris(hydroxymethyl)propane

• Pier Alexandre Champagne,
• Alexandre Saint-Martin,
• Mélina Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2013, 9, 2451–2456, doi:10.3762/bjoc.9.283

• agent, which means we could potentially use the triol as an additive rather than a solvent. Altogether, this strategy would represent a unique metal-free and unprecedented small-molecule-mediated activation of C–F bonds. Herein, we report the feasibility of this concept for the amination of benzylic

Bis(benzylamine) monomers: One-pot preparation and application in dendrimer scaffolds for removing pyrene from aqueous environments

• Olivia N. Monaco,
• Sarah C. Tomas,
• Meghan K. Kirrane and
• Amy M. Balija

Beilstein J. Org. Chem. 2013, 9, 2320–2327, doi:10.3762/bjoc.9.266

• hybrid dendrimers could be isolated and used in different solvent environments without being degraded. Due to their hydrophobic periphery and larger size, hybrid dendrimers 11–13 were envisioned as potential scaffolds to encapsulate small molecule organic pollutants such as polycyclic aromatic

Activation of cryptic metabolite production through gene disruption: Dimethyl furan-2,4-dicarboxylate produced by Streptomyces sahachiroi

• Dinesh Simkhada,
• Huitu Zhang,
• Shogo Mori,
• Howard Williams and
• Coran M. H. Watanabe

Beilstein J. Org. Chem. 2013, 9, 1768–1773, doi:10.3762/bjoc.9.205

• Dinesh Simkhada Huitu Zhang Shogo Mori Howard Williams Coran M. H. Watanabe Texas A&M University, Department of Chemistry, College Station, TX 77843, USA 10.3762/bjoc.9.205 Abstract At least 65% of all small molecule drugs on the market today are natural products, however, re-isolation of

Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

• Andreas Gansäuer,
• Meriam Seddiqzai,
• Tobias Dahmen,
• Rebecca Sure and
• Stefan Grimme

Beilstein J. Org. Chem. 2013, 9, 1620–1629, doi:10.3762/bjoc.9.185

• from the experimental value by only 0.5 kcal mol−1. This deviation (about 5%) is within the typical error limits of DFT-D3 and the experimental methods. In passing it is noted that the D3-dispersion correction to the barrier even for this relatively small molecule is substantial (decrease by 0.7 kcal