Atom transfer radical polymerization.
About: This article is published in Chemical Reviews.The article was published on 2001-09-12. It has received 6927 citations till now. The article focuses on the topics: Reversible addition−fragmentation chain-transfer polymerization & Chain transfer.
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TL;DR: In this article, a review of recent mechanistic developments in the field of controlled/living radical polymerization (CRP) is presented, with particular emphasis on structure-reactivity correlations and "rules" for catalyst selection in ATRP, for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerisation (SFRP), including organic and transition metal persistent radicals.
2,869 citations
TL;DR: In this article, the authors focused on temperature and pH responsive polymer systems and additionally the other stimuli-based responsive polymers will be assessed, which is more helpful to design new approaches because the basic concepts and mechanisms are systematically connected.
2,233 citations
TL;DR: The current status and future perspectives in atom transfer radical polymerization (ATRP) are presented in this paper, with a special emphasis on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP.
Abstract: Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.
2,188 citations
TL;DR: A review of living radical polymerization achieved with thiocarbonylthio compounds by a mechanism of reversible addition-fragmentation chain transfer (RAFT) is presented in this article.
Abstract: This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.
2,127 citations
TL;DR: A new iron(III) halide-promoted aza-Prins cyclization between γ,δ-unsaturated tosylamines and aldehydes provides six-membered azacycles in good to excellent yields.
Abstract: A new iron(III) halide-promoted aza-Prins cyclization between γ,δ-unsaturated tosylamines and aldehydes provides six-membered azacycles in good to excellent yields. The process is based on the consecutive generation of γ-unsaturated-iminium ion and further nucleophilic attack by the unsaturated carbon−carbon bond. Homoallyl tosylamine leads to trans-2-alkyl-4-halo-1-tosylpiperidine as the major isomer. In addition, the alkyne aza-Prins cyclization between homopropargyl tosylamine and aldehydes gives 2-alkyl-4-halo-1-tosyl-1,2,5,6-tetrahydropyridines as the only cyclic products. The piperidine ring is widely distributed throughout Nature, e.g., in alkaloids,1 and is an important scaffold for drug discovery, being the core of many pharmaceutically significant compounds.2,3 The syntheses of these type of compounds have been extensively studied in the development of new drugs containing six-membered-ring heterocycles.4 Reactions between N-acyliminium ions and nucleophiles, also described as amidoalkylation or Mannich-type condensations, have been frequently used to introduce substituents at the R-carbon of an amine.5 There are several examples that involve an intramolecular attack of a nucleophilic olefin into an iminium cation for the construction of a heterocyclic ring system.6 Traditionally, the use of hemiaminals or their derivatives as precursors of N-acyliminium intermediates has been a common two-step strategy in these reactions.6a Among this type of cyclization is the aza-Prins cyclization,7 which uses alkenes as intramolecular nucleophile. However, cy† X-ray analysis. E-mail address: malopez@ull.es. (1) (a) Fodor, G. B.; Colasanti, B. Alkaloids: Chemical and Biological PerspectiVes; Pelletier, S. W., Ed.; Wiley: New York, 1985; Vol. 23, pp 1-90. (b) Baliah, V.; Jeyarama, R.; Chandrasekaran, L. Chem. ReV. 1983, 83, 379-423. (2) Watson, P. S.; Jiang, B.; Scott, B. Org. Lett. 2000, 2, 3679-3681. (3) Horton, D. A.; Bourne, G. T.; Smythe, M. L. Chem. ReV. 2003, 103, 893-930. (4) Buffat, M. G. P. Tetrahedron 2004, 60, 1701-1729 and references therein. (5) Speckamp, W. N.; Moolenaar, M. J. Tetrahedron 2000, 56, 3187- 3856 and references therein. (6) (a) Hiemstra, H.; Speckamp, W. N. In ComprehensiVe Organic Synthesis; Trost, B. M., Fleming, O., Heathcock, C. H., Eds.; Pergamon: New York, 1991; Vol. 2, pp 1047-1081. (b) Speckamp, W. N.; Hiemstra, H. Tetrahedron 1985, 41, 4367-4416. (7) (a) Dobbs, A. P.; Guesne, S. J. J.; Hursthouse, M. B.; Coles, S. J. Synlett 2003, 11, 1740-1742. (b) Dobbs, A. P.; Guesne, S. J. J.; Martinove, S.; Coles, S. J.; Hursthouse, M. B. J. Org. Chem. 2003, 68, 7880-7883. (c) Hanessian, S.; Tremblay, M.; Petersen, F. W. J. Am. Chem. Soc. 2004, 126, 6064-6071 and references therein. (d) Dobbs, A. P.; Guesne, S. J. Synlett 2005, 13, 2101-2103. ORGANIC
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4,185 citations
TL;DR: An extension of ATRA to atom transfer radical addition, ATRP, provided a new and efficient way to conduct controlled/living radical polymerization as mentioned in this paper, using a simple alkyl halide, R-X (X = Cl and Br), as an initiator and a transition metal species complexed by suitable ligand(s), M t n /L x, e.g., CuX/2,2'-bipyridine, as a catalyst.
Abstract: An extension of atom transfer radical addition, ATRA, to atom transfer radical polymerization, ATRP, provided a new and efficient way to conduct controlled/living radical polymerization. By using a simple alkyl halide, R-X (X = Cl and Br), as an initiator and a transition metal species complexed by suitable ligand(s), M t n /L x , e.g., CuX/2,2'-bipyridine, as a catalyst, ATRP of vinyl monomers such as styrenes and (meth)acrylates proceeded in a living fashion, yielding polymers with degrees of polymerization predetermined by Δ[M]/[I] 0 up to M n ≃ 10 5 and low polydispersities, 1.1 < M w /M n < 1.5. The participation of free radical intermediates was supported by analysis of the end groups and the stereochemistry of the polymerization. The general principle and the mechanism of ATRP are elucidated. Various factors affecting the ATRP process are discussed.
1,628 citations
TL;DR: Atom transfer radical polymerization (ATRP) is one of the most successful methods to polymerize styrenes, (meth)acrylates and a variety of other monomers in a controlled fashion, yielding polymers with molecular weights predetermined by the ratio of the concentrations of consumed monomer to introduced initiator and with low polydispersities as discussed by the authors.
1,189 citations