Superstructures with cyclodextrins: chemistry and applications III

• Gerhard Wenz and
• Eric Monflier

Beilstein J. Org. Chem. 2016, 12, 937–938, doi:10.3762/bjoc.12.91

• has been achieved in the synthesis of CD polyrotaxanes. The one-pot and one-step polyrotaxane synthesis of β-CDs was performed in aqueous solution by employing a click reaction [7] as well as by radical copolymerization [8]. Slide-ring gels, synthesized by the group of K. Ito through the crosslinking

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• copolymerization of aqueous acrylamide, acrylamide substituted β-CD and N-adamantyl-acrylamide gives a β-CD- and adamantyl-substituted poly(acrylamide) which forms a hydrogel as shown in Figure 21 [108]. When a portion of the hydrogel is cut in two and both halves are brought back into close contact, the cut

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

• in shape, size and chemical functionality is achieved due to the presence of the target molecule during the polymerization process (Scheme 1). Initially the target molecules form a complex with the cyclodextrin followed by a copolymerization of the imprinted monomers with the crosslinker. 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

• aqueous media to evaluate them as luminescent markers of biological molecules. The production of metal-cation-based anion exchange membranes from ROMP polymers was first reported by Tew et al. [57]. The ROMP reaction, induced here by the Grubbs 2nd generation catalyst, implied the copolymerization of a

• )s. Lanthanide-containing polymers Recently, new polynorbornenes of type 53, functionalized with terpyridine and carbazole moieties and integrating a europium complex in the pendant chains, were described by Rozhkov et al. [67]. They were obtained by a metathesis copolymerization with Grubbs 3rd

Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

• Yulia I. Denisova,
• Maria L. Gringolts,
• Alexander S. Peregudov,
• Liya B. Krentsel,
• Ekaterina A. Litmanovich,
• Arkadiy D. Litmanovich,
• Eugene Sh. Finkelshtein and
• Yaroslav V. Kudryavtsev

Beilstein J. Org. Chem. 2015, 11, 1796–1808, doi:10.3762/bjoc.11.195

• way to unsaturated multiblock statistical copolymers. Their structure can be controlled by the amount of catalyst, mixture composition, and reaction time. It is remarkable that this goal can be achieved with a catalyst that is not suitable for ring-opening metathesis copolymerization of norbornene and

• noteworthy that the reaction is readily mediated by the 1st generation Grubbs’ catalyst Cl2(PCy3)2Ru=CHPh (Gr-1), which is not suitable for metathesis ring-opening copolymerization of NB and COE. Our approach makes it possible to synthesize statistical multiblock NB-COE copolymers containing up to 50% of

• Vestenamer® [17], is a semicrystalline rubber applied as a polymer processing aid for extrusion, injection molding etc. Though easily homopolymerized, NB and COE hardly enter metathesis copolymerization [18][19] because of the much higher activity of NB possessing a considerably more strained bicyclic

Peptide–polymer ligands for a tandem WW-domain, an adaptive multivalent protein–protein interaction: lessons on the thermodynamic fitness of flexible ligands

• Katharina Koschek,
• Vedat Durmaz,
• Oxana Krylova,
• Marek Wieczorek,
• Shilpi Gupta,
• Martin Richter,
• Alexander Bujotzek,
• Christina Fischer,
• Rainer Haag,
• Christian Freund,
• Marcus Weber and
• Jörg Rademann

Beilstein J. Org. Chem. 2015, 11, 837–847, doi:10.3762/bjoc.11.93

• -hydroxypropyl)methacrylamide) (pHPMA) possesses a C2 repeating unit with three fully rotatable bonds, which should convey – compared to the other polymers employed in this study – high backbone flexibility to this carrier. Reactive pHPMA was prepared in a copolymerization of HPMA and the thioester-containing

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

• Tor E. Kristensen

Beilstein J. Org. Chem. 2015, 11, 446–468, doi:10.3762/bjoc.11.51

• variety of proline polymers and proline amphiphiles, on large scale, from hydroxyproline (Scheme 9) [46]. The work was later extended into a generalized system for polymeric immobilization of proline, prolineamide, diarylprolinol and imidazolidinone chiral organocatalysts by copolymerization of a set of

• -load homopolymers by solution copolymerization [46][47], crosslinked polymer microspheres by dispersion copolymerization [47], crosslinked polymer beads by suspension copolymerization [47][48], catalytic core–shell micelles (nanoreactors) [68], hydrophobic nanogel particles by emulsion polymerization

Functionalized branched EDOT-terthiophene copolymer films by electropolymerization and post-polymerization “click”-reactions

• Miriam Goll,
• Adrian Ruff,
• Erna Muks,
• Felix Goerigk,
• Beatrice Omiecienski,
• Ines Ruff,
• Rafael C. González-Cano,
• Juan T. Lopez Navarrete,
• M. Carmen Ruiz Delgado and
• Sabine Ludwigs

Beilstein J. Org. Chem. 2015, 11, 335–347, doi:10.3762/bjoc.11.39

• dicyanovinylene-substituted cyclopentabithiophene and EDOT [23], we recently presented the copolymerization of EDOT and the branched unit 2,2’:3’,2’’-terthiophene (3T) [24]. Additional functionalities, such as ions, can be introduced either by direct attachment of the functional moieties to the monomers or via

• modified bithiophene followed by bipyrrole monomers [38]. In some cases the direct polymerization of ionically modified monomers remains problematic: this was for example reported in the case of sulfonic acid modified pyrrole, where film deposition was only possible when a copolymerization with pristine

• the latter case the water contact angles could be gradually varied. We here present the electrocopolymerization of EDOT-N3 with the branched terthiophene 2,2’:3’,2’’-terthiophene and the post-polymerization into an ionically modified copolymer. Only recently, we reported on the copolymerization of 3T

Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin

• Jun Terao,
• Yohei Konoshima,
• Akitoshi Matono,
• Hiroshi Masai,
• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2014, 10, 2800–2808, doi:10.3762/bjoc.10.297

• CD [11], and (III) copolymerization of the thus-formed pseudorotaxane with linker molecules [12]. These polymers are soluble in water but generally insoluble in organic solvents; this is because the hydrophilic CD covers the organic soluble π-conjugated polymer chains [13]. Uncovered sites are also

Host–guest-driven color change in water: influence of cyclodextrin on the structure of a copper complex of poly((4-hydroxy-3-(pyridin-3-yldiazenyl)phenethyl)methacrylamide-co-dimethylacrylamide)

• Nils Retzmann,
• Gero Maatz and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 2480–2483, doi:10.3762/bjoc.10.259

• tyramine (1) was selectively methacrylated at room temperature followed by a diazotation coupling with 3-aminopyridine (4) leading to N-(4-hydroxy-3-(pyridin-3-yldiazenyl)phenethyl)methacrylamide (5). Subsequently, the azo dye containing polymer 7 was synthesized through free radical copolymerization of 5

The effect of permodified cyclodextrins encapsulation on the photophysical properties of a polyfluorene with randomly distributed electron-donor and rotaxane electron-acceptor units

• Aurica Farcas,
• Ana-Maria Resmerita,
• Pierre-Henri Aubert,
• Flavian Farcas,
• Iuliana Stoica and
• Anton Airinei

Beilstein J. Org. Chem. 2014, 10, 2145–2156, doi:10.3762/bjoc.10.222

• of approaches were examined, e.g., copolymerization [7][8][9][10][11], end-capping with sterically hindered groups [12], introduction of donor (D) and acceptor (A) moieties, to form statistically [13][14] or alternating D–A units in the main chain [15][16][17][18]. The coupling of D–A units has been

Influence of cyclodextrin on the UCST- and LCST-behavior of poly(2-methacrylamido-caprolactam)-co-(N,N-dimethylacrylamide)

• Alexander Burkhart and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 1951–1958, doi:10.3762/bjoc.10.203

• synthesized from methacryloyl chloride (3) and racemic α-amino-ε-caprolactam (2). Copolymerization of 4 with N,N-dimethylacrylamide (5) was carried out by a free-radical mechanism using 2,2’-azobis(2-methylpropionitrile) (AIBN) as an initiator. The new copolymers show a lower critical solution temperature

• -amino-ε-caprolactam (2) was obtained according to literature via cyclocondensation of L-lysine (1) [15]. Through amidation of the primary amine (2) with methacryloyl chloride (3) the polymerizable 2-methacrylamido-caprolactam (4) was obtained (Scheme 1) [14]. Free radical copolymerization of 4 in

• temperature as a function of the amount of N,N-dimethylacrylamide (5) in the copolymers 6a–i. Synthesis of monomer 2-methacrylamido-caprolactam (4) and copolymers 6a–i based on 4 and N,N-dimethylacrylamide (5). Monomer amount of 4 and 5 for the copolymerization of copolymers 6a–i. Different amounts of

Comparing kinetic profiles between bifunctional and binary type of Zn(salen)-based catalysts for organic carbonate formation

• Carmen Martín and
• Arjan W. Kleij

Beilstein J. Org. Chem. 2014, 10, 1817–1825, doi:10.3762/bjoc.10.191

• are the efforts from Coates and co-workers [44] and the kinetic studies described by the group of Williams [45]. In each of these latter cases a binuclear mechanism was proposed for the copolymerization reaction of CO2 and epoxide, establishing a second-order dependence for mononuclear Zn complex 7

Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts

• Jong Yeob Jeon,
• Seong Chan Eo,
• Jobi Kodiyan Varghese and
• Bun Yeoul Lee

Beilstein J. Org. Chem. 2014, 10, 1787–1795, doi:10.3762/bjoc.10.187

• , 1.05–1.5). Because of the extremely high activity of 1, high-molecular-weight polymers were generated (Mn up to 170,000 and 350,000 for the PO/PA copolymerization and PO/CO2/PA terpolymerization, respectively). The terpolymers bearing a substantial number of PA units (fPA, 0.23) showed a higher glass

• with epoxides [1][2][3][4][5][6]. The pioneering work for this copolymerization was introduced by Inoue in 1969 [7]. Eventually, a highly active and efficient catalyst was developed based on the concept of combining (salen)Co(III) units with quaternary ammonium salts in a molecule [8][9][10][11][12

• copolymerization, significant numbers of ether linkages were generated through consecutive PO incorporation [28]. When PA (1.00 g) and PO (10.4 g) were reacted using catalyst 1 (3.0 mg; 1/PA/PO = 1:3,750:100,000) at 80 °C for 3 h, 100% conversion of PA was achieved (entry 1 in Table 1). The 1H NMR spectrum

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• can be divided in two broad categories depending on the presence of polymerizable groups. When polymerizable groups are present, the fire-resistant molecule can be included in polymers by copolymerization or can act as a crosslinking agent. This type of compounds is also employed for the surface

Oligomeric epoxide–amine adducts based on 2-amino-N-isopropylacetamide and α-amino-ε-caprolactam: Solubility in presence of cyclodextrin and curing properties

• Julian Fischer and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 2803–2811, doi:10.3762/bjoc.9.315

• [5]. The Tc can be influenced for example through copolymerization with hydrophobic or hydrophilic comonomers and further through supramolecular interactions of these comonomers with cyclodextrins (CD) [6][7][8][9][10]. Generally, CDs are water soluble and their ability of forming inclusion complexes

Micro-flow synthesis and structural analysis of sterically crowded diimine ligands with five aryl rings

• Shinichiro Fuse,
• Nobutake Tanabe,
• Akio Tannna,
• Yohei Konishi and
• Takashi Takahashi

Beilstein J. Org. Chem. 2013, 9, 2336–2343, doi:10.3762/bjoc.9.268

• ligands exerted high polymerization activity in the ethylene homopolymerization and copolymerization of ethylene with polar monomers. Keywords: amidine formation; diimine; flow chemistry; polymerization; Introduction The design of a ligand is a key step in the development of new catalysts because the

• detailed structural study. Herein, we report an efficient micro-flow synthesis and structural analysis of sterically crowded 1,2,3,4,5-pentaaryl-1,3,5-triazapenta-1,4-diene ligands 3b and 3c, and their use in the copolymerization of ethylene and polar monomers. According to the previous report, 1,2,3,4,5

• homopolymerization nor copolymerization of ethylene with polar monomers by using the catalysts derived from N-aryl-1,3,5-triazapenta-1,4-dienes 1–3 have been reported [18][19]. Thus, we tested the polymerization activity of the catalyst 12 in the copolymerization of ethylene with 5-norbornen-2-ol (NBO) and ethyl

Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

• Quynh Pham Bao Nguyen and
• Taek Hyeon Kim

Beilstein J. Org. Chem. 2013, 9, 2113–2119, doi:10.3762/bjoc.9.248

• . Unexpectedly, racemization occurred under these cleavage conditions to produce the corresponding chiral alcohol and ester in 80% and 77% ee, respectively. Synthesis of NCPS-supported 2-imidazolidinone chiral auxiliary 3 through direct copolymerization of 2-imidazolidinone derived monomer 2 with styrene

Polymeric redox-responsive delivery systems bearing ammonium salts cross-linked via disulfides

• Christian Dollendorf,
• Martin Hetzer and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 1652–1662, doi:10.3762/bjoc.9.189

• polycationic system was synthesized via copolymerization of N,N-diethylacrylamide (DEAAm) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). N,N’-bis(4-chlorobutanoyl)cystamine was used as disulfide-containing cross-linker to form networks by the quaternization of tertiary amine groups. The insoluble cationic

• medical applications. Results and Discussion Synthesis of cross-linked hydrogels in solution and inclusion-release investigations of embedded dyes The copolymerization of DEAAm and DMAEMA was carried out in ethyl acetate as solvent using different concentrations (25–50 wt %) and monomer ratios (1:1 and 5

• -linked discs with CL 1 and CL 2. Results for the copolymerization of DEAAm and DMAEMA using different monomer ratios. Results for oscillatory measurements of polymer discs containing CL 1 and / or CL 2 after immersion in different solvents. Results for the determination of swelling degree Q and glass

Stability of SG1 nitroxide towards unprotected sugar and lithium salts: a preamble to cellulose modification by nitroxide-mediated graft polymerization

• Guillaume Moreira,
• Laurence Charles,
• Mohamed Major,
• Florence Vacandio,
• Yohann Guillaneuf,
• Catherine Lefay and
• Didier Gigmes

Beilstein J. Org. Chem. 2013, 9, 1589–1600, doi:10.3762/bjoc.9.181

• , nanocrystals, etc. ) [2][13]. Working under homogeneous conditions allows for following the kinetics of the grafting copolymerization by size-exclusion chromatography (SEC) or NMR for instance. This is of crucial importance to prove the living/controlled character of a polymerization performed by a CLRP

Polymerization of novel methacrylated anthraquinone dyes

• Christian Dollendorf,
• Susanne Katharina Kreth,
• Soo Whan Choi and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 453–459, doi:10.3762/bjoc.9.48

• suppressed by using inert gas or adequate compounds such as 5-aminopentane-1-ol, for example [27]. Polymerization and photosensitivity of the synthesized monomeric dyes 6, 9 and 10 By way of example for copolymerization of two monomeric dyes, 9 or 10 were copolymerized with 2-hydroxyethylmethacrylate (2-HEMA

New enzymatically polymerized copolymers from 4-tert-butylphenol and 4-ferrocenylphenol and their modification and inclusion complexes with β-cyclodextrin

• Adam Mondrzyk,
• Beate Mondrzik,
• Sabrina Gingter and
• Helmut Ritter

Beilstein J. Org. Chem. 2012, 8, 2118–2123, doi:10.3762/bjoc.8.238

• transistors [22]. Attempts to polymerize 2 in the presence of enzymes have been carried out by several research groups but lead to undesired, electrochemically inactive products [23]. Nevertheless, the copolymerization of 2 and 4-tert-butylphenol (3) to obtain electrochemically active products has not been

• copolymerization of 4-ferrocenylphenol with 4-tert-butylphenol. The 4-ferrocenylphenol obviously tolerates the oxidative environment of H2O2. Furthermore, ortho–ortho- and oxy-ortho-connected phenol monomers were found. However, the free hydroxy groups were subjected to alkylation with propargyl bromide and

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

Influence of cyclodextrin on the solubility of a classically prepared 2-vinylcyclopropane macromonomer in aqueous solution

• Helmut Ritter,
• Jia Cheng and
• Monir Tabatabai

Beilstein J. Org. Chem. 2012, 8, 1528–1535, doi:10.3762/bjoc.8.173

• ß-cyclodextrin in water. Via radical ring-opening copolymerization of 5 and NiPAAm a graft copolymer 8 with a clouding point of 32 °C was synthesized. The branched unsaturated polymer was treated with ozone to cleave the double bonds of the main chain. Keywords: branched poly(NiPAAm); cloud point

• chains. Graft copolymers have found many applications, for example in the field of coatings, adhesives, compatibilizers, emulsifiers or biomaterials [1]. For the synthesis of graft copolymers, free radical copolymerization of macromonomers with suitable low molecular weight vinylmonomers is a widely

• product 6 was formed (Scheme 4). However, GPC of 6 shows only a preferred dimerization of macromonomer 5, which may result from the relative bulky poly(NiPAAm) side chains. Therefore, copolymerization of 5 and NiPAAm was carried out. In this case, as expected, a copolymer 8 was obtained with much higher

Synthesis and characterization of low-molecular-weight π-conjugated polymers covered by persilylated β-cyclodextrin

• Aurica Farcas,
• Ana-Maria Resmerita,
• Andreea Stefanache,
• Mihaela Balan and
• Valeria Harabagiu

Beilstein J. Org. Chem. 2012, 8, 1505–1514, doi:10.3762/bjoc.8.170

• wide emission band during operation [8]. Taking into account the relevant photophysical properties of these organic compounds, new synthetic approaches were developed. Copolymerization of fluorene with thiophene, bithiophene or other aromatic comonomers is an alternative method for tuning the optical

• photophysical properties of PFs by using persilylated γ-CD as a new host molecule [33]. Inclusion of bithiophene into persilylated β-cyclodextrin, randomly methylated β-cyclodextrin, or chemically modified CD derivatives, followed by copolymerization with fluorene monomers results in significant changes in the