Intramolecular glycosylation

• Xiao G. Jia and
• Alexei V. Demchenko

Beilstein J. Org. Chem. 2017, 13, 2028–2048, doi:10.3762/bjoc.13.201

• attempt to simplify the synthesis of the non-symmetrical tethers, a highly trendy triazole-forming click chemistry was combined with rigid spacers by the Schmidt group. α,α’-Dibromo ortho- and meta-xylene-derived rigid spacers were used in this application, and this approach allowed to investigate the

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks

• Sushil K. Maurya and
• Rohit Rana

Beilstein J. Org. Chem. 2017, 13, 1106–1118, doi:10.3762/bjoc.13.110

• potential of the new eco-compatible approach for the macrocyclic library generation. Keywords: carbohydrate; click chemistry; diversity-oriented synthesis; macrocycles; ring-closing metathesis; Introduction Macrocycles offer very complex molecular architectures with a diverse range of ring sizes decorated

Interactions between shape-persistent macromolecules as probed by AFM

• Johanna Blass,
• Jessica Brunke,
• Franziska Emmerich,
• Cédric Przybylski,
• Vasil M. Garamus,
• Artem Feoktystov,
• Roland Bennewitz,
• Gerhard Wenz and
• Marcel Albrecht

Beilstein J. Org. Chem. 2017, 13, 938–951, doi:10.3762/bjoc.13.95

• end groups were prepared starting from diacetylene-modified cyclodextrin monomers by a combined Glaser coupling/click chemistry approach. Structural perfection of the neutral CD polymers and inclusion complex formation with ditopic and monotopic guest molecules were proven by MALDI–TOF and UV–vis

• connection of one CD moiety at each phenylene unit. Based on the stiffness of the polymer chain self-passivation of CD polymer modified surfaces is reduced to a minimum. Furthermore, the ethynyl end groups are easily functionalized by click chemistry. Isothermal titration calorimetry (ITC), fluorescence

• than one polymer molecule might be involved. Conclusion In conclusion, regular water-soluble shape-persistent CD polymers based on poly(phenylene butadiynylene) were prepared by a straightforward Glaser coupling/click chemistry approach, which can be attached to planar silicon surfaces as well as AFM

Synthesis of D-manno-heptulose via a cascade aldol/hemiketalization reaction

• Yan Chen,
• Xiaoman Wang,
• Junchang Wang and
• You Yang

Beilstein J. Org. Chem. 2017, 13, 795–799, doi:10.3762/bjoc.13.79

• evaluation of carbohydrate–lectin interactions by conjugation with fluorescent quantum dots via click chemistry [13][14]. Besides, differentially protected D-manno-heptulose building blocks could serve as valuable precursors for the synthesis of C-glycosides [15][16]. The known synthesis of D-manno-heptulose

Fast and efficient synthesis of microporous polymer nanomembranes via light-induced click reaction

• Qi An,
• Youssef Hassan,
• Xiaotong Yan,
• Peter Krolla-Sidenstein,
• Tawheed Mohammed,
• Mathias Lang,
• Stefan Bräse and
• Manuel Tsotsalas

Beilstein J. Org. Chem. 2017, 13, 558–563, doi:10.3762/bjoc.13.54

• induced thiol–yne click reaction. Using this reaction, we could greatly enhance the CMP nanomembrane synthesis and further broaden the variability of the LbL approach. Keywords: click chemistry; conjugated microporous polymers (CMPs); microporous materials; nanomembranes; thin films; thiol–yne coupling

• catalyst-free thiol–yne coupling (TYC) reaction. TYC has gained large attention as a representative of the click chemistry concept [17]. In the TYC reaction, usually a photoinitiator creates thiyl radicals [18][19][20], which react with nearby alkyne moieties to form covalent sulfur–carbon bonds and vinyl

• . The growth rate of roughly 1 nm per reaction cycle is in the same order as the previously described LbL synthesis of CMP nanomembranes using CuAAC click chemistry [16]. Synthesis of freestanding CMP nanomembranes In order to produce freestanding CMP nanomembranes, we coated the CMP thin films on

Investigation of the action of poly(ADP-ribose)-synthesising enzymes on NAD⁺ analogues

• Sarah Wallrodt,
• Edward L. Simpson and
• Andreas Marx

Beilstein J. Org. Chem. 2017, 13, 495–501, doi:10.3762/bjoc.13.49

• -synthesising enzymes ARTD1, ARTD2, ARTD5 and ARTD6. By varying the site and size of the NAD+ modification, suitable probes were identified for each enzyme. This report provides guidelines for choosing analogues for studying poly(ADP-ribose)-synthesising enzymes. Keywords: ARTD; click chemistry; NAD+; poly(ADP

Solid-phase enrichment and analysis of electrophilic natural products

• Frank Wesche,
• Yue He and
• Helge B. Bode

Beilstein J. Org. Chem. 2017, 13, 405–409, doi:10.3762/bjoc.13.43

• entomopathogenic Photorhabdus bacteria. Keywords: azides; click chemistry; enrichment; electrophilic natural products; epoxides; glidobactin; Photorhabdus; stilbenes; Introduction Microorganisms are a major source for novel natural products and the subsequent development of new drugs for all kinds of

Versatile synthesis of end-reactive polyrotaxanes applicable to fabrication of supramolecular biomaterials

• Atsushi Tamura,
• Asato Tonegawa,
• Yoshinori Arisaka and
• Nobuhiko Yui

Beilstein J. Org. Chem. 2016, 12, 2883–2892, doi:10.3762/bjoc.12.287

• functional PRXs and can be applied to the fabrication of PRX-based supramolecular biomaterials. Keywords: azide group; biomaterials; click chemistry; cyclodextrin; polyrotaxane; Introduction Polyrotaxanes (PRXs) are a class of interlocked polymers that consist of an inclusion complex of cyclodextrins (CDs

• obtained from Sigma-Aldrich (St. Louis, MO, USA). Dibenzocyclooctyne-fluor 488 (DF488) was obtained from Click Chemistry Tools (Scottsdale, AZ, USA). Other solvents were obtained from Kanto Chemicals (Tokyo, Japan). Characterization of PRXs SEC was performed out on an HLC-8120 system (Tosoh, Tokyo, Japan

Chemical probes for competitive profiling of the quorum sensing signal synthase PqsD of Pseudomonas aeruginosa

• Michaela Prothiwa,
• Dávid Szamosvári,
• Sandra Glasmacher and
• Thomas Böttcher

Beilstein J. Org. Chem. 2016, 12, 2784–2792, doi:10.3762/bjoc.12.277

• protein reactive groups, which have been reported to exhibit selectivity for active site cysteines [19] (Supporting Information File 1, Figure S1). Each probe was equipped with a terminal alkyne handle for in-gel analysis by fluorescence tagging via click chemistry with a corresponding rhodamine azide

• Escherichia coli BL21 followed by affinity purification by an ÄKTA chromatography system equipped with a StrepTrap HP column. The individual probes were incubated with purified PqsD for 30 min and a rhodamine fluorescent reporter tag was appended by click chemistry. The remaining non-covalently bound probe

• followed by click chemistry with the fluorophore. A decreasing labelling intensity at increasing NEM concentrations indicates that NEM also blocks the active site cysteine Cys112 at concentrations above 5 µM and thereby prevents covalent attachment of the probe to PqsD (Figure 3D). We were thus interested

A versatile route to polythiophenes with functional pendant groups using alkyne chemistry

• Xiao Huang,
• Li Yang,
• Rikard Emanuelsson,
• Jonas Bergquist,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 2682–2688, doi:10.3762/bjoc.12.265

• alkyne chemistry. Its usefulness is demonstrated by a series of functionalized polythiophene derivatives that were obtained by pre- and post-electropolymerization transformations, provided by the synthetic ease of the Sonogashira coupling and click chemistry. Keywords: electropolymerization; functional

• of such functionalization using a Sonogashira cross-coupling [26] and an azide–alkyne Huisgen cycloaddition [27]. One of the advantages of the cross-coupling and click chemistry is that it allows for reaction conditions tolerant for nearly all of the above mentioned functional groups. Additionally

• , these functionalizations require only readily available starting materials. A related concept, i.e., attachment of a terminal alkyne moiety to the polymerizable thiophene derivative ProDOT, an EDOT analogue, and its utilization for “click“ chemistry has been reported [28]. However, this involved an

Beta-hydroxyphosphonate ribonucleoside analogues derived from 4-substituted-1,2,3-triazoles as IMP/GMP mimics: synthesis and biological evaluation

• Tai Nguyen Van,
• Audrey Hospital,
• Corinne Lionne,
• Lars P. Jordheim,
• Charles Dumontet,
• Christian Périgaud,
• Laurent Chaloin and
• Suzanne Peyrottes

Beilstein J. Org. Chem. 2016, 12, 1476–1486, doi:10.3762/bjoc.12.144

• ]. The inherent flexibility of the corresponding nucleobase-mimics allows to accommodate steric and electronic clashes encountered in protein binding sites and to interact with other amino acids. Another type of fleximers, obtained by a click chemistry approach, was developed by R. H. E. Hudson to obtain

From N-vinylpyrrolidone anions to modified paraffin-like oligomers via double alkylation with 1,8-dibromooctane: access to covalent networks and oligomeric amines for dye attachment

• Daniela Obels,
• Melanie Lievenbrück and
• Helmut Ritter

Beilstein J. Org. Chem. 2016, 12, 1395–1400, doi:10.3762/bjoc.12.133

• access to further potential applications of the corresponding polymers [14][15][16]. Thereby, the electron-rich double bond of N-VP is stable towards nucleophilic attack of the resulting carbanion intermediates. Some alkylated N-VP-based monomers can be used as agents in click chemistry [17] to obtain

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates

• Souad Kachbi-Khelfallah,
• Maelle Monteil,
• Margery Cortes-Clerget,
• Evelyne Migianu-Griffoni,
• Jean-Luc Pirat,
• Olivier Gager,
• Julia Deschamp and
• Marc Lecouvey

Beilstein J. Org. Chem. 2016, 12, 1366–1371, doi:10.3762/bjoc.12.130

• amino functional groups. The azido products will allow us to perform click chemistry to introduce various functionalities. Moreover, the amino derivatives will be easily obtained by reducing the azido group. As previously mentioned, the first step was a selective mono-activation of PEG using para

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

• helices by TFO-MGB conjugates was evaluated by gel-shift experiments. The presence of MGB in these conjugates did not affect the binding parameters (affinity and triplex stability) of the parent TFOs. Keywords: binding affinity; click chemistry; Cu(I)-catalyzed azide–alkyne cycloaddition; pyrrole

• of 1,2,3-triazoles can connect several components in one molecule [25][26]. CuAAC belongs to the class of chemical processes called “click-chemistry” and it is also a biorthogonal reaction because functional groups of natural biopolymers are not affected and do not participate in chemical

• . demonstrated the fluorescent labeling of proteins directly in living cells by copper-free "click chemistry" [29]. Alkyne or azide groups can be inserted into both TFO and MGB using enzymatic or chemical methods during matrix or solid-phase synthesis [2][30][31] or post-synthetically using described conjugation

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

• hyperbranched polystyrene. Chen reported a star-like polymer HBPS-g-PNIPAM in which HBPS was prepared by click chemistry to load small hydrophobic molecules [25]. However, its preparation needs specially designed monomers, the preparation of which is tedious and time-comsuming. Hyperbranched polystyrene (HBPS

From steroids to aqueous supramolecular chemistry: an autobiographical career review

• Bruce C. Gibb

Beilstein J. Org. Chem. 2016, 12, 684–701, doi:10.3762/bjoc.12.69

• using “Click” chemistry [37]. Forming stable complexes for a broad range of guests, the capsules formed by octa-acid are ideal nano-scale (yocto-liter) reaction vessels. Our first foray into this topic relied on collaboration with Vaidhyanathan Ramamurthy, and examined a wide range of photophysics, and

Creating molecular macrocycles for anion recognition

• Amar H. Flood

Beilstein J. Org. Chem. 2016, 12, 611–627, doi:10.3762/bjoc.12.60

• activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted

• philosophy for synthetic design that was derived from Roald Hoffmann’s idea of chemistry being “the same and not the same” [9]. At around this time (2006), click chemistry [10] (Figure 3) had caught my attention for its prevalence but I did not know why it was being used so much. All I could venture was that

• it was an old reaction, the Huisgen cycloaddition, made good (regioselective) with the aid of copper catalysis. Taking that idea on face value, I reasoned that click chemistry was a new and extremely effective way to make 1,2,3-triazoles. It is not often that either new or newly refined reactions

Exploring architectures displaying multimeric presentations of a trihydroxypiperidine iminosugar

• Camilla Matassini,
• Stefania Mirabella,
• Andrea Goti,
• Inmaculada Robina,
• Antonio J. Moreno-Vargas and
• Francesca Cardona

Beilstein J. Org. Chem. 2015, 11, 2631–2640, doi:10.3762/bjoc.11.282

• , Universidad de Sevilla, c/ Prof. García González 1, E-41012, Sevilla, Spain 10.3762/bjoc.11.282 Abstract The synthesis of new multivalent architectures based on a trihydroxypiperidine α-fucosidase inhibitor is reported herein. Tetravalent and nonavalent dendrimers were obtained by means of the click

• chemistry approach involving the copper azide-alkyne-catalyzed cycloaddition (CuAAC) between suitable scaffolds bearing terminal alkyne moieties and an azido-functionalized piperidine as the bioactive moiety. A preliminary biological investigation is also reported towards commercially available and human

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

• Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, P. R. China 10.3762/bjoc.11.276 Abstract The Cu(I)-catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has become a useful tool for the facile formation of 1,2,3-triazoles

• . Specifically, the utility of this reaction has been demonstrated by the synthesis of structurally diverse bi- and bis-1,2,3-triazoles. The present review focuses on the synthesis of such bi- and bistriazoles and the importance of using copper-promoted click chemistry (CuAAC) for such transformations. In

• addition, the application of bitriazoles and the related CuAAAC reaction in different fields, including medicinal chemistry, coordination chemistry, biochemistry, and supramolecular chemistry, have been highlighted. Keywords: bistriazoles; click chemistry; cycloaddition; homogeneous catalysis; oxidative

Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

• Nicolas Desbois,
• Sandrine Pacquelet,
• Adrien Dubois,
• Clément Michelin and
• Claude P. Gros

Beilstein J. Org. Chem. 2015, 11, 2202–2208, doi:10.3762/bjoc.11.239

• are promising contrast agents (CA) in MRI. Keywords: click chemistry; corrole; DOTA; microwave; NOTA; porphyrin; Introduction Magnetic resonance imaging (MRI), positron emission tomography (PET) or single photon emission computed tomography (SPECT) are actually the most commonly used imaging

• (e.g., pH fix at 7 for Cu2+ and pH fix at 3 for Ga3+). The isolated copper and gallium NOTA derivatives 12a,b were characterized by high-resolution mass spectrometry. Scope of the cycloaddition reaction Over the past decade, click chemistry has been applied to the synthesis of a wide variety of

• click chemistry have shown significant advantages over traditional procedures for the modular, rapid, clean, and efficient synthesis of potential radiopharmaceuticals. In this regard, click chemistry has already begun to revolutionize radiopharmaceutical chemistry. The method reported herein provided

Effective ascorbate-free and photolatent click reactions in water using a photoreducible copper(II)-ethylenediamine precatalyst

• Redouane Beniazza,
• Natalia Bayo,
• Florian Molton,
• Carole Duboc,
• Stéphane Massip,
• Nathan McClenaghan,
• Dominique Lastécouères and
• Jean-Marc Vincent

Beilstein J. Org. Chem. 2015, 11, 1950–1959, doi:10.3762/bjoc.11.211

• photogenerated copper(I) being very reactive. On irradiating aqueous reaction mixtures containing 1 mol % of 1 at 365 nm (TLC lamp) for 1 h, click reactions were shown to proceed to full conversion. Keywords: benzophenone photosensitizer; bioconjugation; click chemistry; copper; photoreduction; Introduction

• organic solvents, typically MeOH, THF or toluene. It should be noted that within the last four years, other photoreducible copper(II)-based catalytic systems applied to click chemistry have been reported [15][16][17][18][19][20][21][22][23][24][25][26][27], in particular for the preparation of polymers

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

• -diethynylxanthen-9-one. In addition, a new series of various β-triazole-linked porphyrin–xanthone conjugates and xanthone-bridged triazoloporphyrin dyads were synthesized through click chemistry in moderate to good yields. The preliminary photophysical evaluation of these π-conjugated molecules revealed a

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• 308 in the presence of CuSO4 and sodium ascorbate in acetonitrile/water to deliver the desired cyclophane derivative 309 (56%, Scheme 53). Similarly, a novel BINOL-based cyclophane 310 has been synthesized via click chemistry by incorporating two triazole moieties in the macrocycle [187]. Li and co

Quarternization of 3-azido-1-propyne oligomers obtained by copper(I)-catalyzed azide–alkyne cycloaddition polymerization

• Shun Nakano,
• Akihito Hashidzume and
• Takahiro Sato

Beilstein J. Org. Chem. 2015, 11, 1037–1042, doi:10.3762/bjoc.11.116

• alkynes with a copper(I) catalyst under mild conditions even in the presence of various functional groups [1][2][3]. CuAAC is thus the most important reaction in “click chemistry” [4][5][6][7]. A number of studies have been published on CuAAC, which is applied in a wide range of fields from bio-related