Abstract
The formation of carbon-carbon bonds using free radicals is of utmost importance both in synthetic organic chemistry and in polymer chemistry [1]. The developments that took place during the last decade have considerably modified the view that free radical reactions are commonly uncontrollable. Catalytic systems are now available, that allow radical reactions to be carried out in a precise and controlled manner. In particular, the past few years have witnessed a rapid growth in the development and understanding of controlled radical reactions based on the combination of suitable radical initiators and of transition-metal complexes. For instance, the addition of a polyhalogenated alkane to an olefin, also known as the Kharasch reaction [2], has largely benefited from the replacement of classical radical initiators such as peroxides or UV light by transition- metal complexes that promote a single-electron transfer or a redox-based chain reaction. The latter process is usually referred to as an Atom Transfer Radical Addition (ATRA). In the presence of a high ratio of olefin compared to the halogen derivative, successive insertions of the unsaturated monomer lead to a macromolecular chain, and the net process is known as an Atom Transfer Radical Polymerization (ATRP) (Scheme 1). Among the metals used for promoting ATRP, copper, nickel, iron, and ruthenium tend to display the highest activities, but complexes of rhenium, rhodium, and palladium have also been employed [[3],[4]].
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References
Renaud, P. and Sibi, M. P. (eds.) (2001) Radicals in Organic Synthesis, Wiley-VCH, Weinheim.
Kharasch, M.S., Jensen, E.V., and Urry, W.H. (1945) Addition of carbon tetrachloride and chloroform to olefins, Science 102, 128.
Matyjaszewski, K. and Xia, J. (2001) Atom transfer radical polymerization, Chem. Rev. 101, 2921–2990.
Kamigaito, M., Ando, T., and Sawamoto, M. (2001) Metal-catalyzed living radical polymerization, Chem. Rev. 101, 3689–3746.
Ivin, K.J. and Mol, J.C. (1997) Olefin metathesis and metathesis polymerization, Academic Press, San Diego.
Schuster, M. and Blechert, S. (1997) Olefin metathesis in organic chemistry, Angew. Chem., Int. Ed. 36, 2036–2056.
Fürster, A. (2000) Olefin metathesis and beyond, Angew. Chem., Int. Ed. 39, 3012–3043.
Rouhi, A.M. (2002) Olefin metathesis: big-deal reaction, Chem. Eng. News December 23, 29–33.
Simal, F., Demonceau, A., and Noels, A.F. (1999) Atom transfer radical addition (ATRA) versus atom transfer radical polymerization (ATRP) catalysed by ruthenium complexes, Recent Res. Devel. Org. Chem. 3, 455–464.
Frenzel, U. and Nuyken, O. (2002) Ruthenium-based metathesis initiators: development and use in ring-opening metathesis polymerization, J. Polym. Sci., Part A: Polym. Chem. 40, 2895–2916.
Schwab, P., France, M.B., Ziller, J.W., and Grubbs, R.H. (1995) A series of well-defined metathesis catalysts-Synthesis of [RuCl2(=CHR’)(PR3)2] and its reactions, Angew. Chem., Int. Ed. Engl. 34, 2039–2041.
Trnka, T.M. and Grubbs, R.H. (2001) The development of L2X2Ru=CHR olefin metathesis catalysts: an organometallic success story, Acc. Chem. Res. 34, 18–29.
Stumpf, A.W., Saive, E., Demonceau, A., and Noels, A.F. (1995) Ruthenium-based catalysts for the ring-opening metathesis polymerisation of low-strain cyclic olefins and of functionalised derivatives of norbornene and cyclooctene, Chem. Commun. 1127–1128.
Demonceau, A., Stumpf, A.W., Saive, E., and Noels, A.F. (1997) Novel ruthenium-based catalyst systems for the ring-opening metathesis polymerization of low-strain cyclic olefins, Macromolecules 30, 3127–3136.
Simal, F., Demonceau, A., and Noels, A.F. (1999) Highly efficient ruthenium-based catalytic systems for the controlled free-radical polymerization of vinyl monomers, Angew. Chem., Int. Ed. Engl. 38, 538–540.
Herrmann, W.A. (2002) N-heterocyclic carbenes: a new concept in organometallic catalysis, Angew. Chem., Int. Ed. 41, 1290–1309.
Bourissou, D., Guerret, O., Gabbaï, F.P., and Bertrand, G. (2000) Stable carbenes, Chem. Rev. 100, 39–91.
Simal, F., Delfosse, S., Demonceau, A., Noels, A.F., Denk, K., Kohl, F.J., Weskamp, T., and Herrmann, W.A. (2002) Ruthenium alkylidenes: modulation of a new class of catalysts for controlled radical polymerization of vinyl monomers, Chem. Eur. J. 8, 3047–3052.
Richel, A., Delfosse, S., Cremasco, C., Delaude, L., Demonceau, A., and Noels, A.F. (2003) Ruthenium catalysts bearing N-heterocyclic carbene ligands in Kharasch chemistry, manuscript in preparation.
Delaude, L., Delfosse, S., Richel, A., Demonceau, A., and Noels, A.F. (2003) Tuning of ruthenium N-heterocyclic carbene catalysts for ATRP, manuscript submitted for publication.
Delaude, L., Demonceau, A., and Noels, A.F. (2001) Visible light induced ring-opening metathesis polymerisation of cyclooctene, Chem. Commun. 986–987.
Delaude, L., Szypa, M., Demonceau, A., and Noels, A.F. (2002) New in situ generated ruthenium catalysts bearing N-heterocyclic carbene ligands for the ring-opening metathesis polymerization of cyclooctene, Adv. Synth. Catal. 344, 749–756.
Herrmann, W.A., Köcher, C., Goossen, L.J., and Artus, G.R.J. (1996) Heterocyclic carbenes: a high-yielding synthesis of novel, functionalized N-heterocyclic carbenes in liquid ammonia, Chem. Eur. J. 2, 1626–1636.
Jafarpour, L., Huang, J., Stevens, D., and Nolan, S.P. (1999) (p-cymene)RuLCl2 (L = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and related complexes as ring closing metathesis catalysts, Organometallics 18, 3760–3763.
Kuhn, N. and Kratz, T. (1993) Synthesis of imidazol-2-ylidenes by reduction of imidazole-2(3H)-thiones, Synthesis 561–562.
Arduengo, A.J., III, Krafczyk, R., Schmutzler, R., Craig, H.A., Goerlich, J.R., Marshall, W.J., and Unverzagt, M. (1999) Imidazolylidenes, imidazolinylidenes and imidazolidines, Tetrahedron 55, 14523–14534.
Arduengo, A.J., III, Davidson, F., Dias, H.V.R., Goerlich, J.R., Khasnis, D., Marshall, J., and Prakasha, T.K. (1997) An air stable carbene and mixed carbene “dimers”, J. Am. Chem. Soc. 119, 12742–12749.
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Delaude, L., Delfosse, S., Demonceau, A., Richel, A., Noels, A.F. (2003). Dual Activity of Ruthenium Catalysts in Controlled Radical Reactions and Olefin Metathesis. In: Imamoglu, Y., Bencze, L. (eds) Novel Metathesis Chemistry: Well-Defined Initiator Systems for Specialty Chemical Synthesis, Tailored Polymers and Advanced Material Applications. NATO Science Series, vol 122. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0066-6_7
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DOI: https://doi.org/10.1007/978-94-010-0066-6_7
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