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

• [59][60]. 1.3.3 Deactivation by degenerative transfer: Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most well-established RDRP technique. It was first proposed in 1998 by Commonwealth Scientific and Industrial Research Organization (CSIRO) researchers Chiefari

• radical species and the dormant chains to achieve controlled polymerization of the monomers, allowing all polymer chains to grow nearly simultaneously. The product of RAFT polymerization has a preserved thiocarbonylthio chain end. The polymerization reaction can be continued by adding more monomers

• . Therefore, RAFT is often used to perform chain expansion reactions or to synthesize functionalized multi-block copolymers [62][63][64]. Boyer and co-workers developed a photocatalytically mediated RAFT polymerization, PET-RAFT, which removes the requirement for conventional radical initiators. The reaction

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

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

• supramolecular PDI–CB[7] complex and structures of monomers and the chain transfer agent. Republished with permission of The Royal Society of Chemistry from [48] (“Visible light induced aqueous RAFT polymerization using a supramolecular perylene diimide/cucurbit[7]uril complex” by Y. Yang et al., Polym. Chem

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

• 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

Degenerative xanthate transfer to olefins under visible-light photocatalysis

• Atsushi Kaga,
• Xiangyang Wu,
• Joel Yi Jie Lim,
• Hirohito Hayashi,
• Yunpeng Lu,
• Edwin K. L. Yeow and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2018, 14, 3047–3058, doi:10.3762/bjoc.14.283

• functionalities [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. This concept has also been of particular importance in the field of polymer science, known as reversible addition–fragmentation chain transfer (RAFT) polymerization [15][16]. Mechanistically, the degenerative transfer of xanthates 1 to olefins 2

• absorption [28][29][30][31][32][33][34][35][36][37]. In the area of polymer synthesis, visible-light-induced RAFT polymerization of xanthates with vinyl monomers under blue LED (light-emitting diode) irradiation has been reported [38][39][40][41]. Visible-light-induced single unit monomer insertion of the

• presence of 1a in degassed DMSO recorded at different delay times, respectively (excitation wavelength = 355 nm). UV–vis absorption spectrum of 1a (1 mM solution in DMSO). Degenerative radical transfer of xanthates to olefins. Photocatalytic RAFT polymerization of xanthate 4. Determination of quantum yield

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

• good candidates for photooxidation of vinyl ether initiators. A Ru-based ROMP precatalyst: [Ru(IMesH2)(CF3CO2)(t-BuCN)4)]+ CF3CO2– which is a thermally stable photoredox catalyst has been also proposed in [110]. To finish, the RAFT polymerization can be also extended in a photocontrolled polymerization

• inhibition [112]. Organic photoredox catalysts can also be used to perform a RAFT polymerization, i.e., in [113] trithiocarbonates were proposed as intrinsic photoredox catalysts and RAFT agents. Conclusion In the present paper, some examples of metal and metal-free photoredox catalysts are provided for

One-pot three-component route for the synthesis of S-trifluoromethyl dithiocarbamates using Togni’s reagent

• Azim Ziyaei Halimehjani,
• Martin Dračínský and
• Petr Beier

Beilstein J. Org. Chem. 2017, 13, 2502–2508, doi:10.3762/bjoc.13.247

• intermediates in synthetic organic chemistry [4][5][6][7][8][9][10][11][12], radical chain transfer agents in RAFT polymerization [13], sulfur vulcanization agents in rubber manufacturing [14] and valuable pharmacophores in medicine [15][16][17]. Beside traditional methods, a recent synthesis of

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

• 114 [224] or chitosan 115 [225]. The functionalization of polyacrylamide obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization was also recently reported to produce 116 (Figure 31). However, the conditions of the Moedritzer–Irani reaction induced the hydrolysis of the

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

• monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO2 nanoparticles

• ; ionic liquid; polymeric ionic liquid; RAFT polymerization; Introduction Ionic liquids (ILs) are organic salts. Most of them have a melting point below 100 °C [1][2]. These organic salts do not have the same structure like inorganic salts. This is due to the structure of the ion pairs. They are built of

• treatment at 650 °C of the hybrid material enables the conversion of the polymer shell into a carbon shell. The required block copolymers containing the carbonizable block and the anchoring block, which can bind onto the nanoparticle surface, was synthesized by RAFT polymerization as described in Figure 1b

One-pot synthesis of block-copolyrotaxanes through controlled rotaxa-polymerization

• Jessica Hilschmann,
• Gerhard Wenz and
• Gergely Kali

Beilstein J. Org. Chem. 2017, 13, 1310–1315, doi:10.3762/bjoc.13.127

• act as stoppers for the cyclodextrin rings threaded onto the inner polyisoprene block. Statistical copolyrotaxanes were synthesized by RAFT polymerization as well. RAFT polymerization conditions allow control of the composition as well as the sequence of the constituents of the polymer backbone which

• further effects the CD content and the aqueous solubility of the polyrotaxane. Keywords: block copolymer; cyclodextrin; polyisoprene; polyrotaxane; RAFT polymerization; Introduction Polymer necklaces, i.e., polyrotaxanes and pseudopolyrotaxanes, are supramolecular assemblies comprising polymeric axes

• length as well as statistical distribution of stopper groups along the axis. Herein, we report for the first time a simple one-pot synthesis of polyrotaxanes with control of length and sequence of the polymer axis through RAFT rotaxa-polymerization of isoprene in water. RAFT polymerization was indeed

Glyco-gold nanoparticles: synthesis and applications

• Federica Compostella,
• Olimpia Pitirollo,
• Alessandro Silvestri and
• Laura Polito

Beilstein J. Org. Chem. 2017, 13, 1008–1021, doi:10.3762/bjoc.13.100

• [45][56][57][58]. Prosperi and co-workers coated dodecanthiol AuNPs with manno-calixarenes exploiting hydrophobic interactions, obtaining an efficient targeting against cancer cells [56]. Similarly, a reversible addition−fragmentation chain transfer (RAFT) polymerization approach has been exploited

• of mucin glycoprotein on the surface of cancer cells, which are characterized by a dense presentation of glycans attached to a protein backbone. So, multicopy–multivalent polymeric versions of the tumor-associated α-GalNAc (Tn) antigen, obtained through RAFT polymerization, were prepared and used to

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

• distributed polymers. In the presence of 1,6-hexanediol (C6 diol) which works as a competitive molecule by being included in the α-CD cavity, the reaction yield was lower than that without C6 diol. Keywords: cyclodextrin; radical polymerization; RAFT polymerization; substrate recognition site; supramolecular

• recognition site is introduced to a reversible addition–fragmentation chain transfer (RAFT) polymerization system [65][66][67][68][69]. We have synthesized a chain transfer agent (CTA) bearing the CD moiety (CD-CTA) and have investigated this agent’s polymerization behavior. The polymerization rate constant

• close together during the course of RAFT polymerization. Figure S5a (Supporting Information File 1) shows the crystal structure of β-CD with DMA. β-CD formed a head-to-head dimeric structure in the crystal. Figure S5b shows a schematic diagram of the crystal structure of β-CD/DMA. The stoichiometry of β

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

• because of the radical stabilized by the push–pull substituents. However, with this result it has been shown that the RAFT polymerization is a successful technique for MLA to achieve (co)polymers with narrow dispersities and with almost low molecular weight. Conclusion This first detailed study on the

• [15]. Postulated mechanism of the self-initiation of MLA. Mechanism of RAFT polymerization [24]. SEC data from the polymerization of MLA with different amounts of AIBN (c(MLA) = 1.812 mol L−1in 1,4-dioxane, 15–1 mol % AIBN, 70 °C, polymerization time 2 minutes). Alfrey–Price Q and e values of various

• monomers with styrene as reference system. RAFT polymerization of MLA with different RAFT agents in a ratio of 98.87:1:0.125 ([MLA]/[RAFT]/[AIBN]) (80 wt % 1,4-dioxane, at 70 °C). RAFT homopolymerization of MLA with EMP (80 wt % 1,4-dioxane at 70 °C). RAFT copolymerization of MLA with DMA (0.5 mol % EMP

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

• ) polymerization [15][16], living ionic polymerizations, specifically ring-opening polymerization (ROP) [17], as well as migration insertion polymerization (MIP) [18], acyclic diene metathesis polymerization (ADMET) [19][20] and ring-opening metathesis polymerization (ROMP) [21][22][23][24][25][26][27]. These

Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier

• Yamei Zhao,
• Wei Tian,
• Guang Yang and
• Xiaodong Fan

Beilstein J. Org. Chem. 2014, 10, 2696–2703, doi:10.3762/bjoc.10.284

• micelles by taking advantage of the β-CD cavities. Additionally, longevity and controlled drug release abilities are possible as a result of the PDMAEMA block. Results and Discussion Synthesis of ABC with HBPCSi and β-CD (P3) P1 was first synthesized via a two-step RAFT polymerization and the subsequent

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

• based on a silica core and a shell made of functional polymeric chains with very well controlled structure. The versatility of RAFT polymerization is illustrated by the control of the polymerization of vinylbenzyl chloride (VBC), a highly functional monomer, with the aim of designing silica core–poly

• , and we demonstrate that the exceptional control over their dimensions is achieved by careful tailoring the conditions of the radical polymerization. Keywords: core–shell particles; free radical; grafting; RAFT polymerization; silica; Introduction The versatility of organic free radical chemistry in

• structure of the resulting polymeric chain. Among the many techniques of LRP reported to date, reversible addition–fragmentation chain transfer (RAFT) polymerization is one of the most versatile processes, both in terms of tolerance towards a wide range of monomer functionality and reaction conditions [2

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

• ), 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

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

• , because short and long chains will bind simultaneously, most likely with different affinities and stoichiometries. A quantitative description must inherently suffer from this averaging effect. Results and Discussion Reversible addition–fragmentation chain transfer (RAFT) polymerization [10] and atom