[en] Cobalt-mediated radical coupling (CMRC) is a straightforward approach to the synthesis of symmetrical macromolecules that relies on the addition of 1,3-diene compounds onto polymer precursors preformed by cobalt-mediated radical polymerization (CMRP). Mechanistic features that make this process so efficient for radical polymer coupling are reported here. The mechanism was established on the basis of NMR spectroscopy and MALDI-MS analyses of the coupling product and corroborated by DFT calculations. A key feature of CMRC is the preferential insertion of two diene units in the middle of the chain of the coupling product mainly according to a trans-1,4-addition pathway. The large tolerance of CMRC towards the diene structure is demonstrated and the impact of this new coupling method on macromolecular engineering is discussed, especially for midchain functionalization of polymers. It is worth noting that the interest in CMRC goes beyond the field of polymer chemistry, since it constitutes a novel carbon-carbon bond formation method that could be applied to small organic molecules.
Disciplines :
Chemistry
Author, co-author :
Debuigne, A.
Poli, Rinaldo
De Winter, Julien ; Université de Mons > Faculté des Sciences > Synthèse et spectrométrie de masse organiques
Pascal, Laurent
Gerbaux, Pascal ; Université de Mons > Faculté des Sciences > Synthèse et spectrométrie de masse organiques
Dubois, Philippe ; Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Wathelet, J-P.
Jerome, Ch.
Detrembleur, Christophe
Language :
English
Title :
Cobalt-mediated radical coupling (CMRC): an unusual route to mid-chain-functionalized symmetrical macromolecules
Publication date :
08 February 2010
Journal title :
Chemistry
ISSN :
0947-6539
Publisher :
John Wiley & Sons, United Kingdom
Volume :
16
Issue :
6
Pages :
1799-1811
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S816 - Matériaux Polymères et Composites S836 - Synthèse et spectrométrie de masse organiques
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Commentary :
Lecture en ligne: http://onlinelibrary.wiley.com/doi/10.1002/chem.200902618/pdf
Publié en ligne le 28 décembre 2009
W. A. Braunecker, K. Matyjaszewski, Prog. Polym. Sci. 2007, 32, 93-146.
M. Kamigaito, T. Ando, M. Sawamoto, Chem. Rev. 2001, 101, 3689-3745.
C. J. Hawker, A. W. Bosman, E. Harth, Chem. Rev. 2001, 101, 3661-3688.
V. Sciannamea, R. Jerome, C. Detrembleur, Chem. Rev. 2008, 108, 1104-1126.
C. Barner-Kowollik, Handbook of RAFT Polymerization, WileyVCH, Weinheim, 2008.
G. Moad, E. Rizzardo, S. H. Thang, Acc. Chem. Res. 2008, 41, 1133-1142.
J. Qiu, B. Charleux, K. Matyjaszewski, Prog. Polym. Sci. 2001, 26, 2083-2134.
M. F. Cunningham, Prog. Polym. Sci. 2008, 33, 365-398.
P. B. Zetterlund, Y. Kagawa, M. Okubo, Chem. Rev. 2008, 108, 3747-3794.
A. Debuigne, R. Poli, C. Jerome, R. Jerome, C. Detrembleur, Prog. Polym. Sci. 2009, 34, 211-239.
S. Yamago, Chem. Rev. 2009, 109, 5051-5068.
S. Yurteri, I. Cianga, Y. Yagci, Macromol. Chem. Phys. 2003, 204, 1771-1783.
T. Sarbu, K.-Y. Lin, J. Spanswick, R. R. Gil, D. J. Siegwart, K. Matyjaszewski, Macromolecules 2004, 37, 9694-9700.
T. Sarbu, K.-Y. Lin, J. Ell, D. J. Siegwart, J. Spanswick, K. Matyjaszewski, Macromolecules 2004, 37, 3120-3127.
R. Nagelsdiek, H. Keul, H. Hoecker, e-Polym. 2005, 049.
B. Otazaghine, C. Boyer, J.-J. Robin, B. Boutevin, J. Polym. Sci. Polym. Chem. Ed. 2005, 43, 2377-2394.
B. Nottelet, P. Lacroix-Desmazes, B. Boutevin, Polymer 2007, 48, 50-57.
J. T. Kopping, Z. P. Tolstyka, H. D. Maynard, Macromolecules 2007, 40, 8593-8599.
A. Debuigne, C. Jerome, C. Detrembleur, Angew. Chem. 2009, 121, 1450-1452;
Angew. Chem. Int. Ed. 2009, 48, 1422-1424.
B. B. Wayland, G. Poszmik, S. L. Mukerjee, M. Fryd, J. Am. Chem. Soc. 1994, 116, 7943-7944.
Z. Lu, M. Fryd, B. B. Wayland, Macromolecules 2004, 37, 2686-2687.
A. Debuigne, J.-R. Caille, R. Jerome, Angew. Chem. 2005, 117, 1125-1128;
Angew. Chem. Int. Ed. 2005, 44, 1101-1111
A. Debuigne, J.-R. Caille, C. Detrembleur, R. Jerome, Angew. Chem. 2005, 117, 3505-3508;
Angew. Chem. Int. Ed. 2005, 44, 3439-3442.
S. Maria, H. Kaneyoshi, K. Matyjaszewski, R. Poli, Chem. Eur. J. 2007, 13, 2480-2492.
C.-H. Peng, J. Scricco, S. Li, M. Fryd, B. B. Wayland, Macromolecules 2008, 41, 2368-2373.
A. Debuigne, Y. Champouret, R. Jerome, R. Poli, C. Detrembleur, Chem. Eur. J. 2008, 14, 4046-4059.
H. Kaneyoshi, K. Matyjaszewski, Macromolecules 2006, 39, 2757-2763.
A. Debuigne, N. Willet, R. Jerome, C. Detrembleur, Macromolecules 2007, 40, 7111-7118.
A. Debuigne, C. Michaux, C. Jerome, R. Jerome, R. Poli, C. Detrembleur, Chem. Eur. J. 2008, 14, 7623-7637.
A. Debuigne, J. Warnant, R. Jerome, I. Voets, A. de Keizer, A., M. A. Cohen Stuart, C. Detrembleur, Macromolecules 2008, 41, 2353-2360.
K. Linnemayr, P. Vana, G. Allmaier, Rapid Commun. Mass Spectrom. 1998, 12, 1344-1350.
M. Takayam, J. Am. Soc. Mass Spectrom. 2001, 12, 1044-1049.
Y. Fukuyama, S. Iwamoto, K. Tanaka, J. Mass Spectrom. 2006, 41, 191-201.
A. D. H. Clague, J. A. M.. Van Broekhoven, L. P. Blaauw, Macromo-lecules 1974, 7, 348-354.
G. Van der Velden, C. Didden, T. Veermans, J. Beulen, Macromole- cules 1987, 20, 1252-1256.
T. Ishihara, T. Shiono, Macromolecules 2003, 36, 9675-9677.
J. Brandrup, E. H. Immergut, Polymer Handbook, 4th ed., Wiley-Intersience, New York, 1999.
A. Debuigne, R. Poli, R. Jerome, C. Jerome, C. Detrembleur, ACS Symp. Ser. 2009, 1024, 131-148.
C. J. Cramer, D. G. Truhlar, Ace. Chem. Res. 2008, 41,760.
F. Basolo in Mechanisms of Inorganic Reactions (Ed.: R. F. Gould), American Chemical Society, Washington, 1965.
J. D. Atwood in Inorganic and Organometallic Reaction Mechanisms, Brooks/Cole Publishing, Pacific Grove, 1985.
K. Matyjaszewski, T. P. Davis, Handbook of Radical Polymerization, Wiley, New York, 2002, p. 904.
J..-H. Liu, Y.-G. Li, Y. Lin, Y.-S. Li, J. Polym. Sci. Polym,. Chem. Ed. 2007, 45, 1272-1281.
A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.
Gaussian 03, Revision C. 02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. Montgomery, Jr., J. A., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Ishida, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M, Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K, Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Revision C. 02, Gaussian, Inc., Wallingford, CT, 2004.
