Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• excellent temporal and spatial control of the available photochemical approach makes the technique especially viable for non-solution processes [103]. When a multifunctional thiol is used with diene-functionalized polymers, the approach becomes suitable for chemical crosslinking [103][104], vide infra. It

• in a Ph2C· species and a radical on the polymer (Scheme 19). This reaction may complete in radical coupling or proceed with radical polymerization from the surface [167][168][169], resulting in crosslinked polymers, surface-functionalized polymers, or surface-grafted polymers. RDRP was used to graft

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• macrocycle-based polymeric nanocomposites can produce a better photocatalytic performance compared to the respective monomers and linear analogs due to their more accessible catalytic sites, whereas comparative studies are very limited. In addition, hyperbranched macrocycle-functionalized polymers can act as

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene–phosphine complexes for the Negishi reaction under flow conditions

• Edgar Peris,
• Raúl Porcar,
• María Macia,
• Jesús Alcázar,
• Eduardo García-Verdugo and
• Santiago V. Luis

Beilstein J. Org. Chem. 2020, 16, 1924–1935, doi:10.3762/bjoc.16.159

• under continuous flow conditions. Results and Discussion Scheme 1 summarizes the synthetic approach used for the preparation of the functionalized polymers considered in this work. A commercially available PS-DVB bead-type macroporous chloromethylated polymer 1 (Merrifield resin with 20% DVB and 1.2

Insertion of [1.1.1]propellane into aromatic disulfides

• Robin M. Bär,
• Gregor Heinrich,
• Martin Nieger,
• Olaf Fuhr and
• Stefan Bräse

Beilstein J. Org. Chem. 2019, 15, 1172–1180, doi:10.3762/bjoc.15.114

• ] the compound and its reactions were intensely investigated [10]. Michl et al. synthesized terminally functionalized polymers derived from 1, so-called [n]staffanes, and discussed their application as rigid tectones [11][12]. The characteristic reactivity of 1 emerges from the strained central bond

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• derivatives. The synthetic route for MWCNT-SO3H and its catalytic application for the synthesis of N-substituted pyrrole derivatives. The sulfonic acid-functionalized polymers (P-SO3H) covalently

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

Organic chemistry meets polymers, nanoscience, therapeutics and diagnostics

• Vincent M. Rotello

Beilstein J. Org. Chem. 2016, 12, 1638–1646, doi:10.3762/bjoc.12.161

• with our rather neurotic Weimaraner Trudy, allowing us to get double duty from our toil. Flavoenzyme model system for determining the role of aromatic stacking in flavin redox processes. Reprinted with permission from [10]. Copyright (1997) American Chemical Society. Recognition element-functionalized

• polymers for 'plug and play' modification and self-assembly. Recognition-mediated assembly of nanoparticle–polymer constructs. Reproduced from [24]. Cytosolic delivery of GFP to cells using nanoparticle-stabilized nanocapsules. Adapted with permission from [63]. Copyright (2013) American Chemical Society

Size-controlled and redox-responsive supramolecular nanoparticles

• Raquel Mejia-Ariza,
• Gavin A. Kronig and
• Jurriaan Huskens

Beilstein J. Org. Chem. 2015, 11, 2388–2399, doi:10.3762/bjoc.11.260

• between the multivalent guest-functionalized dendrimers and host-functionalized polymers. At higher ionic strengths, the increased charge screening led to a loss of electrostatic repulsion and therefore to larger aggregates. Optimal self-assembly of the multivalent components was observed at a 1:1

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• to synthesize a number of functionalized polymers. For instance, Müller and Frey used 3,3-bis(hydroxymethyl)oxetane in different blends with 1,8-octanediol and sebacic acid to get polymers with a varied content of oxetane groups (Figure 16). Oxetane is a very acid sensitive moiety, but the mild

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• considered for comparison with systems where the water-soluble phosphane and the polymer were added separately. Depending on the amount of 1, CD-substituted phosphane-functionalized polymers 2b and 2c (Scheme 1) were obtained. To ensure the water solubility of the resulting polymers and remove the remaining

End-group-functionalized poly(N,N-diethylacrylamide) via free-radical chain transfer polymerization: Influence of sulfur oxidation and cyclodextrin on self-organization and cloud points in water

• Sebastian Reinelt,
• Daniel Steinke and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 680–691, doi:10.3762/bjoc.10.61

• synthesis of thermo-, oxidation- and cyclodextrin- (CD) responsive end-group-functionalized polymers, based on N,N-diethylacrylamide (DEAAm). In a classical free-radical chain transfer polymerization, using thiol-functionalized 4-alkylphenols, namely 3-(4-(1,1-dimethylethan-1-yl)phenoxy)propane-1-thiol and

• 3-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane-1-thiol, poly(N,N-diethylacrylamide) (PDEAAm) with well-defined hydrophobic end-groups is obtained. These end-group-functionalized polymers show different cloud point values, depending on the degree of polymerization and the presence of randomly

• Supporting Information File 1, Figures S1 to S4 for the 1H and 13C NMR data). Synthesis of the end-group functionalized polymers. The thiol functionalized 4-alkylphenols (6a and 6b) were used as chain transfer agents (CTA) for the free-radical polymerization of N,N-diethylacrylamide (DEAAm) (7) (see Scheme 2

Towards a biocompatible artificial lung: Covalent functionalization of poly(4-methylpent-1-ene) (TPX) with cRGD pentapeptide

• Lena Möller,
• Christian Hess,
• Jiří Paleček,
• Yi Su,
• Axel Haverich,
• Andreas Kirschning and
• Gerald Dräger

Beilstein J. Org. Chem. 2013, 9, 270–277, doi:10.3762/bjoc.9.33

• foils hampers continuous stirring. When functionalized polymers 8c and 8d were washed by soxhlet treatment (six hours in methanol) no change of the color of the polymer membranes or the extracts was encountered. It must be noted that neither TPX 2 nor functionalized analogues 4, 7a or 7b have an

Imidazole as a parent π-conjugated backbone in charge-transfer chromophores

• Jiří Kulhánek and
• Filip Bureš

Beilstein J. Org. Chem. 2012, 8, 25–49, doi:10.3762/bjoc.8.4

• ) featuring a N-phenylbenzimidazole motif [129]. These materials exhibited their longest absorption maxima λmax at 490–515 and third-order NLO susceptibility χ(3)(3ω;ω,ω,ω) within the range of 1.5 to 2.6 × 10−13 esu (measured by THG at 1064 nm). Variously 4,5-dicyanoimidazole-functionalized polymers were

Valence isomerization of cyclohepta-1,3,5-triene and its heteroelement analogues

• Helen Jansen,
• J. Chris Slootweg and
• Koop Lammertsma

Beilstein J. Org. Chem. 2011, 7, 1713–1721, doi:10.3762/bjoc.7.201

• reactivity perfectly matches the well-established solution-phase chemistry [109]. Using these phosphinidenes [110][111] led to the synthesis of unique P-ligands for catalysis [112][113] as well as to attractive building blocks for the creation of P-functionalized polymers [114][115]. Conclusion The valence

Multistep flow synthesis of vinyl azides and their use in the copper-catalyzed Huisgen-type cycloaddition under inductive-heating conditions

• Lukas Kupracz,
• Jan Hartwig,
• Jens Wegner,
• Sascha Ceylan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2011, 7, 1441–1448, doi:10.3762/bjoc.7.168

• Amberlyst A-26 [26]. Chemically, this reagent behaves like iodine azide (1), but in contrast it is not explosive and is storable for weeks without a substantial loss of activity [27]. In this report, we disclose the first two-step flow synthesis of vinyl azides based on functionalized polymers 5 and 8. The

• trisubstituted alkenes 4h and 4i owing to the observed stereochemistry. Both of the functionalized polymers 5 and 8 are ideally suited for regeneration of the active species by employing simple flushing protocols without having to change the principal setup. Thus, azide-loaded ion-exchange resin 9, which is

• employing two functionalized polymers that served as a packed-bed material inside the reactor. Additionally, we showed that copper-catalyzed vinyl triazole formation of these vinyl azides in the presence of alkynes is possible by using elemental copper as an inductively heatable material. The method avoids

Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers

• Daniel Crespy and
• Katharina Landfester

Beilstein J. Org. Chem. 2010, 6, 1132–1148, doi:10.3762/bjoc.6.130

• Daniel Crespy Katharina Landfester Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany 10.3762/bjoc.6.130 Abstract The miniemulsion technique is a particular case in the family of heterophase polymerizations, which allows the formation of functionalized polymers by

• polymerization or modification of polymers in stable nanodroplets. We present here an overview of the different polymer syntheses within the miniemulsion droplets as reported in the literature, and of the current trends in the field. Keywords: functionalized polymers; heterophase polymerization; miniemulsion

• synthesis of functionalized polymers in miniemulsion can occur either by (co)polymerizing one or several functional monomers, or by the modification of polymers present in the dispersed phase of a miniemulsion. In the latter case, the functionalization can occur by the reaction or the assembly of small

Functionalized polymers: synthesis and properties

• Helmut Ritter

Beilstein J. Org. Chem. 2010, 6, No. 55, doi:10.3762/bjoc.6.55

• functionalized polymers to update the “state of the art” of knowledge in this field. It is therefore a great pleasure to serve as an editor for this series of articles. Helmut Ritter Düsseldorf, May 2010

Polyionic polymers – heterogeneous media for metal nanoparticles as catalyst in Suzuki–Miyaura and Heck–Mizoroki reactions under flow conditions

• Klaas Mennecke and
• Andreas Kirschning

Beilstein J. Org. Chem. 2009, 5, No. 21, doi:10.3762/bjoc.5.21

• heterogeneous supports for palladium(0) nanoparticles is described. These functionalized polymers were incorporated inside a flow reactor and employed in Suzuki–Miyaura and Heck cross couplings under continuous flow conditions. Keywords: Heck–Mizoroki reaction; heterogeneous catalysis; ion exchange resin