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

• radical polymerization is that a limited control of molecular weights and architectures can be achieved due to the slow initiation and rapid termination. In 1956, Szwarc coined the term “living polymerization” in an anionic system [27]. Since then, polymer chemists have been in pursuit for a comparable

Investigation of cationic ring-opening polymerization of 2-oxazolines in the “green” solvent dihydrolevoglucosenone

• Solomiia Borova and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2023, 19, 217–230, doi:10.3762/bjoc.19.21

• polymerization process. Further work will be necessary to establish whether a living polymerization can be achieved by additional adjustments. Keywords: 2-alkyl-2-oxazolines; matrix-assisted laser desorption/ionization mass spectrometry; nuclear magnetic resonance; polymerization kinetics; Introduction

• the dependence of monomer concentration M on t is expected in the case of the living polymerization. The decreases compared with MeOTf at the same temperature. The data obtained from these kinetic investigations are summarized in Table 1. After examining the 1H NMR spectra collected during the

Oxime radicals: generation, properties and application in organic synthesis

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Alexander S. Budnikov and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107

• used in the development of organic magnetic materials [1], organic batteries [2][3][4], in the preparation of polymers by living polymerization [5][6], in the studies of biomolecules and living systems by EPR [7] and NMR [8] techniques. Stable N-oxyl radicals occupy a central place in organic chemistry

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

• rather clear nowadays that the olefin-metathesis reaction is a versatile tool for the synthesis of multiblock copolymers with diverse chemical structures. Due to the rapid progress in the catalyst design for living polymerization, sequential ROMP has become a well-established method of obtaining

Hypervalent iodine compounds for anti-Markovnikov-type iodo-oxyimidation of vinylarenes

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Mikhail A. Syroeshkin,
• Alexander A. Korlyukov,
• Pavel V. Dorovatovskii,
• Yan V. Zubavichus,
• Gennady I. Nikishin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2018, 14, 2146–2155, doi:10.3762/bjoc.14.188

• electrochemical synthesis [2], and as mediators of living polymerization [10][11]. In organic synthesis more stable types of N-oxyl radicals can be used as carbon-centered radical scavengers [12], oxidation catalysts, mainly for conversion of alcohols to carbonyl compounds [11][13][14][15][16][17]. Less stable

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

• 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

• catalysts are active initiators in producing, in a living polymerization manner, well-defined polymers containing Ru in the side chains. Again, the best results were obtained with the Grubbs 3rd generation catalyst. Along this line, Sleiman et al. [56] prepared an array of oxanorbornene monomers tethered

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

• ) investigated in the present study were prepared via a free-radical instead of a living polymerization technique and had a relative low molecular weight, the optical transmission diagrams indicate a relatively sharp transition in a temperature range of 1 °C up to 2 °C as well as a good reversibility upon

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

• carry out a controlled/living polymerization by SG1-based NMP in DMA/LiCl or DMF/LiCl. As expected, with the BlocBuilder MA alkoxyamine as an initiator (Figure 1), the NMP of styrene performed in DMA at 120 °C without LiCl fulfilled the criteria of a controlled polymerization (PDI values < 1.5, linear

• styrene in DMA at 120 °C. Figure 9a and Figure 9b prove that a successful controlled/living polymerization could be achieved in these conditions (linear increase of the number-average molar mass with conversion, PDI values < 1.5, and regular shift of the molar mass distribution) until 40% of conversion

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

• Helga Seyler,
• Jegadesan Subbiah,
• David J. Jones,
• Andrew B. Holmes and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2013, 9, 1492–1500, doi:10.3762/bjoc.9.170

• the polymerization step on addition of the catalyst, Ni(dppp)Cl2, as a solid (Scheme 1a) [6]. As KCTP is a quasi-living polymerization, the product molecular weight can be controlled by adjusting the monomer-to-catalyst ratio [21]. At the start of this study, the aim was to transfer conventional batch

Synthesis and crystal structures of multifunctional tosylates as basis for star-shaped poly(2-ethyl-2-oxazoline)s

• Richard Hoogenboom,
• Martin W. M. Fijten,
• Guido Kickelbick and
• Ulrich S. Schubert

Beilstein J. Org. Chem. 2010, 6, 773–783, doi:10.3762/bjoc.6.96

• initiator was prepared, which yielded a well-defined star-shaped poly(2-ethyl-2-oxazoline) by CROP as demonstrated by SEC with RI, UV and diode-array detectors, as well as by 1H NMR spectroscopy. Keywords: cationic polymerization; crystal structure; living polymerization; star-polymer; tosylate

Synthesis and crossover reaction of TEMPO containing block copolymer via ROMP

• Olubummo Adekunle,
• Susanne Tanner and
• Wolfgang H. Binder

Beilstein J. Org. Chem. 2010, 6, No. 59, doi:10.3762/bjoc.6.59

• achieved extensively via living polymerization methods. Thus, besides acyclic diene metathesis polymerization (ADMET) [2], ring opening metathesis polymerization (ROMP) [3][4][5] is another type of olefin metathesis polymerization that can be used for the synthesis of block copolymers. Early examples of