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

• application of a C–C bond forming synthesis for the PEDOT functionalization by a Sonogashira coupling yielding the first terephthalate functionalized EDOT monomer as well as a viologen unit with symmetrical N-substitution attached to an EDOT core. These new monomers have been successfully electropolymerized

Formose reaction controlled by boronic acid compounds

• Toru Imai,
• Tomohiro Michitaka and
• Akihito Hashidzume

Beilstein J. Org. Chem. 2016, 12, 2668–2672, doi:10.3762/bjoc.12.263

• polymer, respectively (Scheme 1). The copolymer was prepared by radical copolymerization at a molar ratio of 1:10 in monomer feed. The formose reaction was carried out using a solution containing 200 mM formaldehyde and 20 mM calcium hydroxide at 60 °C. Fructose or glyceraldehyde was employed as a

Interactions between cyclodextrins and cellular components: Towards greener medical applications?

• Loïc Leclercq

Beilstein J. Org. Chem. 2016, 12, 2644–2662, doi:10.3762/bjoc.12.261

• neglected. Similar conclusions were made by Paal and Szeijtli [103]. iv) Complexation of nucleic acids Nucleic acids are macromolecules, where the monomer is the nucleotide. Each nucleotide has three components: a 5-carbon sugar, a phosphate group, and a nitrogenous base. These nucleotides are joined by

Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

• Kohei Koyanagi,
• Yoshinori Takashima,
• Takashi Nakamura,
• Hiroyasu Yamaguchi and
• Akira Harada

Beilstein J. Org. Chem. 2016, 12, 2495–2502, doi:10.3762/bjoc.12.244

• functions of supramolecular catalysts. CD derivatives are widely used in radical polymerization to dissolve hydrophobic monomers in aqueous solutions [48][49][50][51][52][53][54] and to control the aggregation of polymers [55][56][57][58]. Although supramolecular catalysts with CDs as monomer recognition

• sites and catalytic active sites have been designed for polymerization reactions, relatively few reports have described a catalytic design in which the catalytic active site does not leave the CD monomer recognition site during the growing step. In a previous design of radical initiators with CDs, the

• radical-initiating end group leaves the CD monomer recognition site [59][60]. With this molecular design, an included monomer is distant from the radical species and cannot be involved in the direct polymerization. Here, we will observe the effect of monomer recognition of CD on polymerization if a

Methylenelactide: vinyl polymerization and spatial reactivity effects

• Judita Britner and
• Helmut Ritter

Beilstein J. Org. Chem. 2016, 12, 2378–2389, doi:10.3762/bjoc.12.232

• polymerization of the cyclic push–pull-type monomer methylenelactide in comparison to the non-cyclic monomer α-acetoxyacrylate is described. The experimental results revealed that methylenelactide undergoes a self-initiated polymerization. The copolymerization parameters of methylenelactide and styrene as well

• -dimethylacrylamide was performed at 70 °C in 1,4-dioxane using AIBN as initiator and 2-(((ethylthio)carbonothioyl)thio)-2-methylpropanoic acid as a transfer agent. Keywords: copolymerization; kinetic study of the radical homopolymerization; push–pull monomer; reversible addition fragmentation chain transfer (RAFT

• copolymerization of MLA with styrene and methyl methacrylate, respectively. The results were compared to the well-known push–pull type monomer α-acetoxyacrylate. Results and Discussion Free-radical polymerization of methylenelactide MLA The push–pull type monomer MLA contains an electron-deficient vinyl group

Isosorbide and dimethyl carbonate: a green match

• Fabio Aricò and
• Pietro Tundo

Beilstein J. Org. Chem. 2016, 12, 2256–2266, doi:10.3762/bjoc.12.218

• -pot, environmental friendly and high yielding. The reactivity of isosorbide with DMC is equally interesting as it can lead to the formation of dicarboxymethyl isosorbide, a potential monomer for isosorbide-based polycarbonate, and dimethyl isosorbide, a high boiling green solvent. The peculiar

• in the highest isolated yield. Dicarboxymethyl isosorbide is also an intermediate of great interest in view of its application as monomer for homo- and co-polycarbonates incorporating the isosorbide subunit. In this prospect, carboxymethylation of isosorbide can be efficiently carried out via DMC

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

• Pierre Boufflet,
• Sebastian Wood,
• Jessica Wade,
• Zhuping Fei,
• Ji-Seon Kim and
• Martin Heeney

Beilstein J. Org. Chem. 2016, 12, 2150–2163, doi:10.3762/bjoc.12.205

• blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation

• behavior avoids any issues of triblock copolymers, and also provides good control over the molecular weight and relative block lengths [24][25][26][27][28][29][30][31]. In addition to enabling the formation of a diblock copolymer via sequential monomer addition, the KCTP can lead to controlled end

• KCTP using a method analogous to that used for thiophene-selenophene block copolymers [26]. Due to the much lower solubility of F-P3OT compared to P3OT, the more soluble P3OT block was grown first from the activated monomer 2, followed by the addition of 4 to the P3OT macroinitiator. Relative block

DNA functionalization by dynamic chemistry

• Zeynep Kanlidere,
• Oleg Jochim,
• Marta Cal and
• Ulf Diederichsen

Beilstein J. Org. Chem. 2016, 12, 2136–2144, doi:10.3762/bjoc.12.203

• , we generated the libraries of reversibly interconverting building blocks – dynamic combinatorial libraries (DCL) (Figure 1). The abasic strand and its complementary template strand are spontaneously assembled into a double helix through Watson–Crick base-pairing and the incoming nucleobase monomer

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• to facilitate work-up, recycling, and purification of products, especially for large-scale preparations. These heterogeneous systems include supported metal oxides and binary oxide mixtures. For example, MoO3/SiO2 and sol–gel MoO3/TiO2 is used for the preparation of diphenyl oxalate monomer (DPO

• intermediate towards the diphenyl carbonate monomer. The first step is the insertion of CO2 into ethylene oxide to give ethylene carbonate, which is catalyzed by onium salts. The second step involves the transesterification of ethylene carbonate with methanol. The reaction is carried out in a continuous

From supramolecular chemistry to the nucleosome: studies in biomolecular recognition

• Marcey L. Waters

Beilstein J. Org. Chem. 2016, 12, 1863–1869, doi:10.3762/bjoc.12.175

• highly amenable to structure–function studies, since only a new monomer must be synthesized, rather than an entirely new receptor. With my interest in trimethyllysine provided a significant problem in which DCC seemed to be a promising solution. It turns out that the main tool for sensing protein post

Synthesis and characterization of benzodithiophene and benzotriazole-based polymers for photovoltaic applications

• Desta Gedefaw,
• Marta Tessarolo,
• Margherita Bolognesi,
• Mario Prosa,
• Renee Kroon,
• Wenliu Zhuang,
• Patrik Henriksson,
• Kim Bini,
• Ergang Wang,
• Michele Muccini,
• Mirko Seri and
• Mats R. Andersson

Beilstein J. Org. Chem. 2016, 12, 1629–1637, doi:10.3762/bjoc.12.160

• interchain π–π stacking, BDT is a widely used electron-rich monomer. Moreover, alkyl or aryl groups can easily be introduced to BDT basic units as side groups to finely tune the properties of the resulting polymers, not only in terms of solubility but also contributing, for example, to extend the π

• PTzBDT-2 (Scheme 1), based on Tz and BDT moieties. The Tz ring was substituted with an asymmetrically branched alkyl side chain and sandwiched between two thiophene rings. The chemical structure of the Tz based monomer was made to be the same in both polymers for the comparative study. On the other hand

Automated glycan assembly of a S. pneumoniae serotype 3 CPS antigen

• Markus W. Weishaupt,
• Stefan Matthies,
• Mattan Hurevich,
• Claney L. Pereira,
• Heung Sik Hahm and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2016, 12, 1440–1446, doi:10.3762/bjoc.12.139

• glucose building block. This monomer did not suffer from a loss of stereocontrol as was observed in the case of the similarly protected GlcA building block. The desired trisaccharide 5 was observed as the main product from the automated synthesis by HPLC analysis (Figure 5). The Lev protecting group had

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

• paraffin-like oligomeric chains bearing polymerizable vinyl moieties. These oligomers were radically crosslinked in bulk with N-VP as co-monomer yielding swellable polymer disks. The vinylic side groups of the N-VP oligomers allow thiol–ene click reactions with 2-aminoethanethiol hydrochloride to obtain

• . However, in contrast to the restricted monoalkylation of N-vinylcaprolactam [24], the five-membered ring of N-VP can be double alkylated in α-position. In this connection, 1-bromo-2-(2-bromoethoxy)ethane was used as alkylation reagent to allow the preparation of a spiro-type monomer [25] due to

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• interplay between ligand exchange and the ammonium salt (Scheme 19) [40]. Based on their findings they proposed a catalytic cycle in which the Brønsted basic dimeric palladium-μ-hydroxo complex 79 is broken up by the amine salt 74, liberating Lewis acidic palladium monomer 80 and free amine. Binding of the

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

• ) prepared through atom transfer radical self-condensing vinyl polymerization (AT-SCVP) was firstly reported in 1996 [26]. It used vinylbenzyl chloride (VBC), which is an important commercially available monomer and its industrial synthesis was started from 1957, as monomer with a self-initiation site [27

• (VBC), a commercially available monomer, as monomer and self-initiator. The feeding ratio of VBC/CuCl/2,2-bipyrene (bpy) was 10:1:2. The 1H NMR spectrum of HBPS showed peaks around 5.7 and 5.2 ppm attributed to double bonds [26][27] as shown in Figure 1B. For AT-SCVP, the polymerization was initiated

• by benzyl chloride of VBC. It was found that each polymer chain was tethered with a double bond and chloride groups. Each monomer inserted into the polymer chain has one initiate site to start propagation of the side chains, which leads to the formation of hyperbranched topology. The broad peak from

Amino-functionalized (meth)acryl polymers by use of a solvent-polarity sensitive protecting group (Br-t-BOC)

• Helmut Ritter,
• Monir Tabatabai and
• Markus Herrmann

Beilstein J. Org. Chem. 2016, 12, 245–252, doi:10.3762/bjoc.12.26

• product. This means that the amino-protecting group is extremely sensitive to decomposition. A third type of monomer was synthesized by reaction of 1a with 1-bromo-2-methylbut-3-en-2-ol (2c) yielding 2-((1-bromo-2-methylbut-3-en-2-yl)oxycarbonylamino)ethyl acrylate (3d, Scheme 3). Although monomer 3d is

• deprotection for 3a,b, 6a,b and 7a,b are summarized in Table 1. As assumed above the molecular dispersed monomer shows the highest reactivity followed by the copolymer. The solvolysis of the protecting group in the homopolymer is relatively slow because of neighboring group formed retarding hydrogen bonds

My maize and blue brick road to physical organic chemistry in materials

• Anne J. McNeil

Beilstein J. Org. Chem. 2016, 12, 229–238, doi:10.3762/bjoc.12.24

• : to evaluate the effect of through-space (rather than through-bond) interactions on a conjugated polymer’s properties. During this project I synthesized some of the most beautiful molecules I have ever seen, with one and two cofacial arenes surrounding the central arene of the monomer (Figure 1) [14

• by our surprising substituent effects on the Diels–Alder regioselectivity in our monomer synthesis. Together we designed a collaborative project to further evaluate these effects. These studies led us to conclude that the π system is relatively unimportant and that substituent effects can instead be

• students Cheryl Moy and Danielle Zurcher evaluated “disassembling” polymers wherein an analyte-mediated end-group cleavage triggers depolymerization, releasing many gelators for each analyte [32][45]. We investigated three different polymeric scaffolds but have not yet successfully polymerized any monomer

Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

• Julia Wappel,
• Roland C. Fischer,
• Luigi Cavallo,
• Christian Slugovc and
• Albert Poater

Beilstein J. Org. Chem. 2016, 12, 154–165, doi:10.3762/bjoc.12.17

• nature [1][2], but exploiting similar strategies for synthetic catalysts is still in its infancy [3][4][5]. Prominent examples in catalytic polymerization [6][7] comprise the regulation of molecular weight by allosteric effects [8][9] or influencing the polymers’ microstructure upon changing the monomer

• years [24][25][26]. The latent initiators are ideal if they have the capacity of storage in combination with the monomer for a long period [27]. Then the reaction only initiates once an appropriate exogenous stimulus is exerted [28][29]. Amongst this important property, the latent initiator should be as

• observed upon heating at 80 °C for 48 h [43]. Catalytic activity The polymerization activity of the complexes was initially tested using dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (5) as the benchmark monomer. Monomer 5 was used because its polymers are not prone to backbiting. Therefore the

Supramolecular structures based on regioisomers of cinnamyl-α-cyclodextrins – new media for capillary separation techniques

• Gabor Benkovics,
• Ondrej Hodek,
• Martina Havlikova,
• Zuzana Bosakova,
• Pavel Coufal,
• Milo Malanga,
• Eva Fenyvesi,
• Andras Darcsi,
• Szabolcs Beni and
• Jindrich Jindrich

Beilstein J. Org. Chem. 2016, 12, 97–109, doi:10.3762/bjoc.12.11

• electrophoresis as additives to the background electrolyte. These new monomer units with a potential to self-organize into supramolecular structures were synthesized via a straightforward one-step synthetic procedure and purified using preparative reversed-phase chromatography allowing a large scale separation of

• the regioisomers. The ability of the monomers to self-assemble was proved by various methods including NMR spectroscopy and dynamic light scattering (DLS). The light scattering experiments showed that the monomer units have distinguishable ability to form supramolecular structures in different

• that the position of the cinnamyl group plays an important role in the intermolecular complex formation. Keywords: capillary electrophoresis; cyclodextrin derivatives; mono-cinnamyl; regioisomers; supramolecular structures; Introduction Supramolecular polymers (SP) are aggregates of monomer units

Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time ¹³C CP-MAS solid-state NMR characterization

• Isabelle Mallard,
• Davy Baudelet,
• Franca Castiglione,
• Monica Ferro,
• Walter Panzeri,
• Enzio Ragg and
• Andrea Mele

Beilstein J. Org. Chem. 2015, 11, 2785–2794, doi:10.3762/bjoc.11.299

• obtained and characterized by solid-state 13C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials

• paper, we described the synthesis of imprinted polymers. The imprinting technique is based on interactions between a template and a suitable functional monomer during the prepolymerization process. Once the template is removed, the resulting product is a cross-linked copolymer matrix with specific

• larger ratio of crosslinker to functional monomer to get insoluble polymers. The deprotonation was carried out in aqueous basic media and imprinting was performed in toluene for 20 min before the polymerization process. After the introduction of toluene, a clear solution was systematically observed. The

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• quite active and tolerant toward the monomer endowed with multiple functionalities (Scheme 1). By precisely controlling the living polymerization process, they succeeded in varying the number of amidoferrocenyl motifs in the polymers within pre-established limits. Such polymers and block copolymers were

• one block contains cobaltocenium units while the other block comprises an organic chain only [50] (Scheme 4). By the same technique, polymer 6 was further copolymerized with a cobaltocenium-BPh4 monomer and a cobaltocenium-Cl monomer affording, respectively, the new diblock copolymers 8 (X = PF6, Y

• application of metallopolymers as heterogeneous macromolecular catalysts for living radical polymerizations, Tang et al. [51] produced the cobalt-containing polymer 10 by ROMP of the norbornene monomer 9, derivatized with triazolyl and cyclopentadienylcobalt-1,3-cyclopentadiene moieties (Scheme 5). The

Enantioselective additions of copper acetylides to cyclic iminium and oxocarbenium ions

• Jixin Liu,
• Srimoyee Dasgupta and
• Mary P. Watson

Beilstein J. Org. Chem. 2015, 11, 2696–2706, doi:10.3762/bjoc.11.290

• high levels of enantioselectivity. This lack is likely due to the multiple possibilities for copper acetylide structures (monomer, dimer, dicopper acetylide, etc.) [18][59][60][61][62][63][64][65]. Careful mechanistic studies to elucidate the structures of chiral copper acetylides and to provide

Synthesis and photophysical characteristics of polyfluorene polyrotaxanes

• Aurica Farcas,
• Giulia Tregnago,
• Ana-Maria Resmerita,
• Pierre-Henri Aubert and
• Franco Cacialli

Beilstein J. Org. Chem. 2015, 11, 2677–2688, doi:10.3762/bjoc.11.288

• was also synthesized by coupling 1 with 2 under similar reaction conditions (Scheme 1). TM-βCD and TM-γCD macrocyclic molecules were prepared according to previously reported procedures [47]. 1·TM-βCD and 1·TM-γCD were synthesized in water by using a 2:1 molar ratio of macrocycles and monomer 1. The

• polyrotaxane exhibits correlation peaks of both H3 and H5 protons of TM-βCD with those methylene protons (Hd) protons of monomer 2, and all the characteristic protons have been identified, Figure 1. Figures S4–S7 in Supporting Information File 1 show the 1H NMR and 13C NMR spectra of 3·TM-γCD and the reference

• 3. The resonance peak of the d proton from monomer 2 is upfield shifted by more than 0.06 ppm in the polyrotaxane 3·TM-βCD compared to those of the non-rotaxane 3 counterpart, as shown in Figure 1 and Figure S4 in Supporting Information File 1. The resonance peaks of a–c and a’–c’ protons of 3·TM

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

• moiety, the CuAAC approach was investigated either on the protected and deprotected iminosugar, with different purification techniques employed in both cases. A monomer reference compound was also synthesized for comparison. Biological evaluation against a panel of eleven commercially available

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η⁵-Cp)Pd(IPr)Cl with (η³-cinnamyl)Pd(IPr)(Cl) and (η³-1-t-Bu-indenyl)Pd(IPr)(Cl)

• Patrick R. Melvin,
• Nilay Hazari,
• Hannah M. C. Lant,
• Ian L. Peczak and
• Hemali P. Shah

Beilstein J. Org. Chem. 2015, 11, 2476–2486, doi:10.3762/bjoc.11.269

• literature method starting from the commercially available Pd(II) dimer (μ-Cl)2Pd2(η3-allyl)2 (Scheme 1) [18]. It is notable that in this synthesis dimeric {(IPr)Pd(Cl)}2(μ-Cl)2 is prepared as an intermediate, followed by treatment with two equivalents of NaCp to generate the monomer Cp. This synthesis makes