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

• polymerization at that time and the rate of propagation was much faster than with TEMPO under the same conditions. 1.3.2 Deactivation by atom transfer: Atom transfer radical polymerization (ATRP) was independently reported by the teams of Matyjaszewski [41] and Sawamoto [42] in 1995. The efficient conduct of

• ATRP relies on the establishment of a reversible activation/deactivation equilibrium reaction between an alkyl halide or halide-like initiator (RX) and a radical species (R·) [43]. During the activation process, the organohalides quickly lose their terminal halogen atoms in the presence of the liganded

• deactivation process. Activation and deactivation reactions are always present throughout the process, and the rate of deactivation must be sufficiently high in order to maintain a low radical concentration to effectively inhibit the termination [44]. The mechanism of ATRP is shown in Scheme 5 [14]. Compared

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• in the formation of H2 and O2 from the water splitting reaction by donating strain-induced electrons and holes [53]. The piezoelectricity obtained upon ultrasonication of BaTiO3 has also been used to trigger and sustain atom transfer radical polymerization (ATRP) reactions of acrylate monomers by

• a collision between the ball and a particle of a chitin sample and (b) mechanical treatment of a particle of a lignin sample in a ring-and-puck mill. (a) Ultrasound-induced ATRP using piezoelectric BaTiO3 and (b) mechanochemical atom transfer radical cyclization (ATRC) using BaTiO3 by ball milling

A two-phase bromination process using tetraalkylammonium hydroxide for the practical synthesis of α-bromolactones from lactones

• Yuki Yamamoto,
• Akihiro Tabuchi,
• Kazumi Hosono,
• Takanori Ochi,
• Kento Yamazaki,
• Shintaro Kodama,
• Akihiro Nomoto and
• Akiya Ogawa

Beilstein J. Org. Chem. 2021, 17, 2906–2914, doi:10.3762/bjoc.17.198

• polymerization (ATRP) reactions and functional polymer synthesis [29][30][31][32][33][34]. Although α-bromo-γ-butyrolactone, which is a five-membered lactone, is easily accessible from the five-membered lactone by some bromination methods [35][36], the bromination method for the six-membered lactone, δ

Exfoliated black phosphorous-mediated CuAAC chemistry for organic and macromolecular synthesis under white LED and near-IR irradiation

• Azra Kocaarslan,
• Zafer Eroglu,
• Önder Metin and
• Yusuf Yagci

Beilstein J. Org. Chem. 2021, 17, 2477–2487, doi:10.3762/bjoc.17.164

• [34][38][39][40]. The use of 2D materials for the photoinitiated electron transfer reactions with CuII catalysts for the photoinduced atom transfer radical polymerization (ATRP) and CuAAC reactions prompted us to develop a new photoredox system that works under NIR irradiation for the CuAAC reaction

• (3C, CH2), 80.83 (3C, C, alkyne). Synthesis of ω-azido terminated polystyrene (PS-Az) ω-Bromo functional polystyrene was synthesized by ATRP according to a reported procedure [48]. In a flask equipped with a magnetic stirrer, PS-Br (1 equiv) and sodium azide (5 equiv) were dissolved in 5 mL DMF. The

Constrained thermoresponsive polymers – new insights into fundamentals and applications

• Patricia Flemming,
• Alexander S. Münch,
• Andreas Fery and
• Petra Uhlmann

Beilstein J. Org. Chem. 2021, 17, 2123–2163, doi:10.3762/bjoc.17.138

Photophysics and photochemistry of NIR absorbers derived from cyanines: key to new technologies based on chemistry 4.0

• Bernd Strehmel,
• Christian Schmitz,
• Ceren Kütahya,
• Yulian Pang,
• Anke Drewitz and
• Heinz Mustroph

Beilstein J. Org. Chem. 2020, 16, 415–444, doi:10.3762/bjoc.16.40

• been in progress. Tailor-made synthesis by photo-ATRP with NIR sensitizers NIR absorbers/sensitizers have also reached the field of polymer synthesis; that is controlled/living radical polymerization (CLRP). This facilitates well-defined polymeric materials with pre-design architectures, predetermined

• polymerization (NMP) processes, reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) [118]. While there has been no report available with NIR-sensitized NMP, there exist a few reports for RAFT polymerization with NIR light [119][120][121]. Recently, ATRP with Cu

• catalyst concentration by continuous regeneration of Cu(I) species using Cu(II) as starting material. These methods include initiators for continuous activator regeneration (ICAR) ATRP, activators regenerated by electron transfer (ARGET) ATRP, supplemental activators and reducing agent (SARA) ATRP, and

Olefin metathesis in multiblock copolymer synthesis

• Maria L. Gringolts,
• Yulia I. Denisova,
• Eugene Sh. Finkelshtein and
• Yaroslav V. Kudryavtsev

Beilstein J. Org. Chem. 2019, 15, 218–235, doi:10.3762/bjoc.15.21

• polymerization (ATRP) and сlick reactions for the precise synthesis of amphiphilic ABCBA-type block copolymers (Scheme 4) [63]. A more facile “one-pot” procedure for the synthesis of an end-functionalized conjugated multiblock copolymer with PFV main chain was accomplished by combining olefin metathesis and

• such as ATRP, RAFT, click-reaction, and so on, which permit to gain certain control over the final copolymer structures. The most recent approach to the multiblock copolymer synthesis implements the macromolecular cross-metathesis reaction, which is still poorly studied. For this method, the simplicity

Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region

• Aude-Héloise Bonardi,
• Frédéric Dumur,
• Guillaume Noirbent,
• Jacques Lalevée and
• Didier Gigmes

Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282

• to go to its excited state and then oxidized by the initiator or the dormant species (R-Mn-Br) [102]. To regenerate the PC, a single electron transfer reaction must be involved as shown in Scheme 8. Through these single electron transfer processes, photo-ATRP has been successfully achieved (ATRP

• transition metal complexes” [106]. In this mechanism, the catalyst is the most important component: it determines the equilibrium constant between the active and dormant species which is directly linked to the distribution of chain lengths [107]. As photoredox catalysts for ATRP applications, copper(II

• )-complexes have been widely used. For example, bis(1,10-phenanthroline)copper(I) (abbreviated Cu(phen)22+) is reported in ref [37] as an efficient photoredox catalyst for ATRP upon a simple household blue LED. Ir-based photoredox catalyst are also efficient in this mechanism such as tris(2-phenylpyridinato

Synthesis of naturally-derived macromolecules through simplified electrochemically mediated ATRP

• Paweł Chmielarz,
• Tomasz Pacześniak,
• Katarzyna Rydel-Ciszek,
• Izabela Zaborniak,
• Paulina Biedka and
• Andrzej Sobkowiak

Beilstein J. Org. Chem. 2017, 13, 2466–2472, doi:10.3762/bjoc.13.243

• ) (PtBA) side arms was synthesized via a simplified electrochemically mediated ATRP (seATRP), utilizing only 78 ppm by weight (wt) of a catalytic CuII complex. To demonstrate the possibility of temporal control, seATRP was carried out utilizing a multiple-step potential electrolysis. The rate of the

• ; quercetin-based macromolecules; Introduction In the last decade, there have been increasing research activities in the use of atom transfer radical polymerization (ATRP) to prepare naturally-derived star-like polymers [1][2][3][4]. Considering this method, naturally-occurring polymers can be synthesized

• macromolecules [37][38][39], widely used as dental adhesives, controlled release devices, coatings, and in pharmaceutical industry [40][41]. Therefore, it is expected that these synthesized naturally-derived macromolecules can become key elements of antifouling coatings and drug delivery systems. ATRP is one of

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

• Sadaf Hanif,
• Bernd Oschmann,
• Dmitri Spetter,
• Muhammad Nawaz Tahir,
• Wolfgang Tremel and
• Rudolf Zentel

Beilstein J. Org. Chem. 2017, 13, 1693–1701, doi:10.3762/bjoc.13.163

• about controlled/living radical polymerization, like nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer polymerization (RAFT) [2]. In general, by controlled radical polymerization techniques it is possible to prepare

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

• characterization of HBPS and HBPE-g-PDMAEMA The target polymer HBPS-g-PDMAEMA was prepared through AT-SCVP and following ATRP strategies as shown in Figure 1A. HBPS with hyperbranched topology was prepared through atom transfer radical self-condensing vinyl polymerization (AT-SCVP) by using vinylbenzyl chloride

• obtained HBPS was used as macro initiator to polymerize DMAEMA through ATRP. The comparison of GPC curves in Figure 1C showed that the curve of the graft copolymer was shifted to less elution time. The GPC results show Mn of HBPS to be 4.4 kg/mol with a molecular weight distribution of 1.85 and Mn of HBPS

• -g-PDMAEMA is 151.3 kg/mol with a molecular weight distribution of 2.84. The molecular weight of HBPS-g-PDMAEMA is bigger than HBPS, which demonstrated that HBPS-containing chlorine atoms successfully initiated the ATRP of DMAEMA, which resulted in HBPS-g-PDMAEMA. Figure 1B shows the 1H NMR spectrum

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

• synthesis of these targets presently accessible through controlled and living polymerization techniques including controlled radical polymerizations (CRP) such as atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP) and reversible addition–fragmentation chain transfer (RAFT

Self-assemblies of γ-CDs with pentablock copolymers PMA-PPO-PEO-PPO-PMA and endcapping via atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine

• Jing Lin,
• Tao Kong,
• Lin Ye,
• Ai-ying Zhang and
• Zeng-guo Feng

Beilstein J. Org. Chem. 2015, 11, 2267–2277, doi:10.3762/bjoc.11.247

• Jing Lin Tao Kong Lin Ye Ai-ying Zhang Zeng-guo Feng School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China 10.3762/bjoc.11.247 Abstract Pentablock copolymers PMA-PPO-PEO-PPO-PMA synthesized via atom transfer radical polymerization (ATRP) were self

• pentablock copolymer chain to generate single-chain-stranded loose-fit PPRs and showed no characteristic channel-like crystal structure. All the self-assembly processes of the pentablock copolymers resulted in the formation of hydrogels. After endcapping via in situ ATRP of 2-methacryloyloxyethyl

• phosphorylcholine (MPC), these single-chain-stranded loose-fit PPRs were transformed into conformational identical polyrotaxanes (PRs). The structures of the PPRs and PRs were characterized by means of 1H NMR, GPC, 13C CP/MAS NMR, 2D 1H NOESY NMR, FTIR, WXRD, TGA and DSC analyses. Keywords: ATRP; γ-CD; double

Loose-fit polypseudorotaxanes constructed from γ-CDs and PHEMA-PPG-PEG-PPG-PHEMA

• Tao Kong,
• Lin Ye,
• Ai-ying Zhang and
• Zeng-guo Feng

Beilstein J. Org. Chem. 2014, 10, 2461–2469, doi:10.3762/bjoc.10.257

• knowledge, self-assembled PPRs from γ-CDs with the bulkier poly(2-hydroxyethyl methacrylate) (PHEMA)-flanked block copolymers have not yet been reported. Herein, a pentablock copolymer PHEMA-PPO-PEO-PPO-PHEMA is prepared via atom transfer radical polymerization (ATRP) in DMF, and allowed to self-assemble

• -sectional areas, PHEMA is attached to both ends of PPO-PEO-PPO by ATRP to yield a pentablock PHEMA-PPO-PEO-PPO-PHEMA copolymer. It is then used to investigate the possibility of self-assembly with γ-CDs [17][18]. The synthetic pathway for the pentablock copolymer is shown in Scheme 2. To shed light on the

• , 2-bromoisobutyryl group. Furthermore, there is a hydrolytic side reaction of end-capped bromine in the in situ aqueous ATRP of NIPAAm that can reduce the chain end functionality and the efficiency of future chain end modification. Thus, Cu(I)Cl/PMDETA was chosen as catalyst and DMF as solvent for

Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

• Rajesh Munirathinam,
• Roberto Ricciardi,
• Richard J. M. Egberink,
• Jurriaan Huskens,
• Michael Holtkamp,
• Herbert Wormeester,
• Uwe Karst and
• Willem Verboom

Beilstein J. Org. Chem. 2013, 9, 1698–1704, doi:10.3762/bjoc.9.194

• polymerization (ATRP) initiator was covalently anchored on silicon oxide substrates [20]. Then, a solution of styrene sulfonate in methanol/water (1:3) in the presence of 2-2’-bipyridyl and CuBr, was used to grow the PSS polymer brushes by means of ATRP. After activation of the polymer brushes with 1 M HCl, they

• reactivating the microreactor with GaCl3. Gallium-catalyzed dehydration of cinnamaldehyde oxime (1). General scheme for anchoring of initiator, ATRP of styrene sulfonate, activation, and reaction with gallium chloride. Thickness of gallium-functionalized PSS polymer brushes on a flat silicon oxide surface

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

• polysaccharide backbone. This last method is the most convenient one as it is less sensitive to steric hindrance problems, which can limit the grafting process. The development of controlled/living radical polymerization (CLRP) techniques, such as atom transfer radical polymerization (ATRP) [4][5][6][7

• efficient to solubilize polysaccharides, is DMA in the presence of LiCl (generally 5 to 10 wt % versus DMA) [15]. This system has already been reported to successfully solubilize cellulose before grafting modification by ATRP in dimethyl sulfoxide (DMSO) [16], but not in the case of NMP yet. Indeed, to our

The synthesis of well-defined poly(vinylbenzyl chloride)-grafted nanoparticles via RAFT polymerization

• John Moraes,
• Kohji Ohno,
• Guillaume Gody,
• Thomas Maschmeyer and
• Sébastien Perrier

Beilstein J. Org. Chem. 2013, 9, 1226–1234, doi:10.3762/bjoc.9.139

• polymerization (ATRP) [30][31]. It has, therefore, been used in a variety of systems as a precursor to glycopolymer stars [29], photo- and pH-responsive nanoparticles [30], nanofibres [28], comb, graft and star polymers [27], and triblock copolymers [26]. While there have been reports of the (co)polymerization

• be expected if ATRP were used to polymerize VBC) can be avoided [27][32]. For the purposes of this study, high-molecular-weight chains (ca. 20 to 100 kg/mol) are of importance, as the ability to grow high-molecular-weight chains from the surface of the silica particles allows us to increase the

Cyclodextrin-induced host–guest effects of classically prepared poly(NIPAM) bearing azo-dye end groups

• Gero Maatz,
• Arkadius Maciollek and
• Helmut Ritter

Beilstein J. Org. Chem. 2012, 8, 1929–1935, doi:10.3762/bjoc.8.224

• controlled conditions such as reversible addition–fragmentation chain-transfer polymerization (RAFT) or atom-transfer radical polymerization (ATRP) [14][15][16]. However, up to now, only a little is known about the preparation of dye-end-group-labeled polymers by using classical free-radical polymerization

Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

• Yannick Borguet,
• Xavier Sauvage,
• Guillermo Zaragoza,
• Albert Demonceau and
• Lionel Delaude

Beilstein J. Org. Chem. 2010, 6, 1167–1173, doi:10.3762/bjoc.6.133

• compound was first reported in 2005 by Severin et al. who successfully used it as a catalyst for atom transfer radical addition (ATRA) and cyclization (ATRC) reactions [4][5]. In 2007, we further extended its application field to the related process of atom transfer radical polymerization (ATRP) [2

• ][13][14], ATRP [15][16][17][18], cyclopropanation [19], dihydroxylation [20], hydrogenation [21][22][23], hydrovinylation [24], isomerization [25][26][27][28], oxidation [29], or Wittig reactions [30], to name just a few [31]. In this contribution, we investigate the tandem catalysis of RCM/ATRC

• had already established that monometallic ruthenium–indenylidene complexes were able to promote the ATRA and ATRP of vinyl monomers [36][37]. In a tandem RCM/ATRC process, it is, however, very unlikely for the indenylidene species to remain unaltered in solution after the metathesis step. Indeed

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

• -radical polymerization, but also simple functionalization of the chain end by the initiator. Miniemulsion systems were found to be suitable to conduct controlled radical polymerizations [48][49][50][51] including atom transfer radical polymerization (ATRP), reversible addition fragmentation transfer (RAFT

• ), degenerative iodine transfer [48], and nitroxide mediated polymerization (NMP). ATRP in miniemulsions was recently described in several reviews [52][53]. The kinetics of RAFT polymerization in miniemulsion has been discussed by Tobita [54] and thus no detailed description is required here. Surfactant monomer

Hybrid biofunctional nanostructures as stimuli-responsive catalytic systems

• Gernot U. Marten,
• Thorsten Gelbrich and
• Annette M. Schmidt

Beilstein J. Org. Chem. 2010, 6, 922–931, doi:10.3762/bjoc.6.98

• chlorine groups for subsequent initiation of atom transfer radical polymerization (ATRP). Oligo(ethylene glycol) methyl ether methacrylates with different length of the hydrophilic side chain are used as the main monomer to generate a hydrophilic polymer shell with tunable critical solution behavior in

• introduction of carboxy functions to the polymer shell by surface-initiated ATRP involving (meth)acrylic acid is hindered by catalyst poisoning, resulting in a loss of reaction control. To overcome this, the protection of the carboxy group is useful [45], and in our approach, we employed succinimidyl

• methacrylate (SIMA) as a methacrylic acid derivative suitable for ATRP [46][47][48]. We have initially investigated the copolymerization behavior of the two monomers in model copolymerization experiments in solution, to ensure proper incorporation of the functional groups and stability of the active ester

Novel multi-responsive P2VP-block-PNIPAAm block copolymers via nitroxide-mediated radical polymerization

• Cathrin Corten,
• Katja Kretschmer and
• Dirk Kuckling

Beilstein J. Org. Chem. 2010, 6, 756–765, doi:10.3762/bjoc.6.89

• the last few years. This includes nitroxide-mediated radical polymerization (NMRP) [18], atom transfer radical polymerization (ATRP) [19][20] and radical addition fragmentation chain transfer procedures (RAFT) [21][22]. The controlled polymerization of styrene, and analogous monomers such as 2

• -vinylpyridine (2VP), is one point of interest because at pH values lower than 5 it is possible to protonate the 2VP units and hence P2VP can be used as a pH-responsive component. Several techniques such as NMRP, ATRP and RAFT led to well-defined homo and block copolymers of different architectures whose

• poly(tert-butylmethacrylate) (PtBMA) as the hydrophobic compounds [25]. The design of bi-responsive narrowly distributed block copolymers consisting of NIPAAm and acrylic acid (AAc) was also feasible [26]. By the use of the ATRP catalyst system of tris(2-dimethylaminoethyl)amine (Me6TREN) and Cu(I

RAFT polymers for protein recognition

• Alan F. Tominey,
• Julia Liese,
• Sun Wei,
• Klaus Kowski,
• Thomas Schrader and
• Arno Kraft

Beilstein J. Org. Chem. 2010, 6, No. 66, doi:10.3762/bjoc.6.66

• -transfer radical polymerization (ATRP) have become extremely useful tools for the controlled synthesis of a wide range of polymers and could solve both problems by formation of monodisperse functionalized polymer chains of equal length, without the need for final polymer-analogous deprotection. So far

• , there have been no reports of the successful use of ATRP with acrylamides. In contrast, RAFT can be used in a variety of solvents and, most importantly, it is compatible with NIPAM [11][12]. For this reason, RAFT was chosen in this paper as the preferred method for controlled synthesis of linear