Dendrimers are well-defined macromolecules3 that can be used
in various fields of nanosciences such as nanoreactors,4 molec-
ular micelles,5 drug vectors,6 sensors,7 green catalysts,8 su-
pramolecular electronics,9 and light-harvesting devices.10
“Click” Glycodendrimers Containing 27, 81, and
243 Modified Xylopyranoside Termini
Je´re´my Camponovo,† Caroline Hadad,‡ Jaime Ruiz,†
Eric Cloutet,§ Sylvain Gatard,‡ Jacques Muzart,‡
Sandrine Bouquillon,*,‡ and Didier Astruc*,†
(1) (a) Muzart, J.; He´nin, F.; Estrine, B.; Bouquillon, S. 2001 Fr patent
0116363 and PCT Int. Appl. WO 03 053987; Chem. Abstr. 2003, 139, 54601.
(b) Estrine, B.; Bouquillon, S.; He´nin, F.; Muzart, J. Eur. J. Org. Chem. 2004,
2914. (c) Estrine, B.; Bouquillon, S.; He´nin, F.; Muzart, J. Green Chem. 2005,
7, 219. (d) Hadad, C.; Damez, C.; Bouquillon, S.; Estrine, B.; He´nin, F.; Muzart,
J.; Pezron, I.; Komunjer, L. Carbohydr. Res. 2006, 341, 1938. (e) Damez, C.;
Estrine, B.; Bessmertnykh, A.; Bouquillon, S.; He´nin, F.; Muzart, J. J. Mol.
Catal. A 2006, 244, 93. (f) Estrine, B.; Bouquillon, S.; He´nin, F.; Muzart, J.
Appl. Organomet. Chem. 2007, 21, 945. (g) Damez, C.; Bouquillon, S.; Harakat,
D.; He´nin, F.; Muzart, J.; Pezron, I.; Komunjer, L. Carbohydr. Res. 2007, 342,
154.
Institut des Sciences Mole´culaires (ISM), UMR CNRS No.
5255, UniVersite´ Bordeaux I, 351 Cours de la Libe´ration,
33405 Talence Cedex, France, Institut de Chimie
Mole´culaire (ICMR), UMR CNRS No. 6229, UFR Sciences,
UniVersite´ Reims-Champagne-Ardenne, Moulin de la Housse,
BP 1039 boite no. 44, 51687 Reims Cedex 2, France, and
Laboratoire de Chimie des Polyme`res Organiques (LCPO),
UMR CNRS No. 5629, UniVersite´ Bordeaux 1, ENSCPB, 16
AVenue Pey Berland 33607 Pessac, France
(2) Hadad, C.; Majoral, J.-P.; Muzart, J.; Caminade, A.-M.; Bouquillon, S.
Tetrahedron Lett. 2009, 59, 1902.
(3) (a) Ardoin, N.; Astruc, D. Bull. Soc. Chim. Fr. 1995, 132, 875. (b)
Newkome, G. R.; Moorefield, C. N.; Vo¨gtle, F. Dendrimers and Dendrons.
Concepts, Syntheses, Applications; Wiley-VCH: Weinheim, Germany, 2001. (c)
Dendrimers and Other Dendritic Polymers, Fre´chet, J. M. J., Tomalia, D. A.,
Eds.; Wiley: New York, 2002. (d) Ornelas, C.; Ruiz, J.; Belin, C.; Astruc, D.
J. Am. Chem. Soc. 2009, 131, 590.
(4) (a) Hecht, S.; Fre´chet, J. M. J. Angew. Chem., Int. Ed. 2001, 40, 74. (b)
Niu, Y.; Crooks, R. M. C. R. Chimie 2003, 6, 1049. (c) Scott, R. W. J.; Wilson,
O. M.; Crooks, R. M. J. Phys. Chem. B 2005, 109, 692. (d) Bosman, A. W.;
Janssen, H. M.; Meijer, E. W. Chem. ReV. 1999, 99, 1665.
d.astruc@ism.u-bordeaux1.fr;
sandrine.bouquillon@uniV-reims.fr
ReceiVed March 16, 2009
(5) (a) Newkome, G. R.; Yao, Z.; Baker, G. R.; Gupta, V. K. J. Org. Chem.
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25, 31. (c) Newkome, G. R. Pure Appl. Chem. 1998, 70, 2337. (d) Tomalia,
D. A.; Naylor, A. M.; Goddard, W. A., III. Angew. Chem., Int. Ed. Engl. 1990,
29, 138. (e) Newkome, G. R.; Moorefield, C. N.; Baker, G. R.; Behera, R. K.;
Escamillia, G. H.; Saunders, M. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 917.
(f) Pistolis, G.; Malliaris, A.; Paleos, C. M.; Tsiourvas, D. Langmuir 1997, 13,
5970. (g) Naylor, A. M.; Goddard, W. A., III.; Kiefer, G. E.; Tomalia, D. A.
J. Am. Chem. Soc. 1989, 111, 2339.
(6) (a) Astruc, D. C. R. Acad. Sci. 1996, 322, 757. (b) Jansen, J. F. G. A.; de
Brabander-van den Berg, E. M. M.; Meijer, E. W. Science 1999, 266, 1226. (c)
Liu, M.; Kono, K.; Fre´chet, J. M. J. Controlled Release 2000, 85, 85. (d) Malik,
N.; Wiwattanapatapee, R.; Klopsch, R.; Lorenz, K.; Frey, H.; Weener, J. W.;
Meijer, E. W.; Paulus, W.; Duncan, R. J. Controlled Release 2000, 65, 133. (e)
Guillot-Nieckowski, M.; Eisler, S.; Diederich, F. New J. Chem. 2007, 31, 1111.
(f) Caminade, A.-M.; Turrin, C.-O.; Majoral, J.-P. Chem.sEur. J. 2008, 14,
7422.
(7) (a) Daniel, M.-C.; Ruiz, J.; Astruc, D. J. Am. Chem. Soc. 2003, 125,
1150. (b) Daniel, M.-C.; Ruiz, J.; Nlate, S.; Blais, J.-C.; Astruc, D. J. Am. Chem.
Soc. 2003, 125, 2617. (c) Astruc, D. Pure Appl. Chem. 2003, 75, 461. (d) Daniel,
M.-C.; Ruiz, J. Chem. Commun. 2004, 2637. (e) Ashton, P. R.; Balzani, V.;
Clemente-Leon, M.; Colonna, B.; Credi, A.; Jayaraman, N.; Raymo, F. M.;
Stoddart, J. F.; Venturi, M. Chem.sEur. J. 2002, 8, 673.
A series of large glycodendrimers containing 27, 81, and
243 terminal modified xylose branches from the first (G1-
27) to the third generation (G3-243) were synthesized from
2′-azidoethyl 2,3,4-tri-O-acetyl-ꢀ-D-xylopyranoside and alky-
nyl-terminated dendrimers by “click” chemistry that is
confirmed to be an excellent method to obtain large glyco-
dendrimers exemplified by the use of modified xylose. The
1
dendrimers were first characterized by H NMR, 13C{1H}
NMR, elemental analysis, and IR spectroscopy. The size
progression in the series was also demonstrated using both
DOSY NMR and size exclusion chromatography (SEC), the
latter technique showing the good polydispersity of all the
dendrimers. The size measured by dynamic light scattering
(DLS) for the dendrimer G3-243 is close to that obtained by
the DOSY NMR method.
(8) (a) Oosterom, G. E.; Reek, J. N. H.; Kamer, P. C. J.; van Leeuwen,
P. W. N. M. Angew. Chem., Int. Ed. 2001, 40, 1828. (b) Astruc, D.; Chardac, F.
Chem. ReV. 2001, 101, 2991. (c) Kleij, A. W.; Ford, A.; Jastrzebski, J. T. B. H.;
van Koten, G. In Dendrimers and Other Dendritic Polymers; Fre´chet, J. M. J.,
Tomalia, D. A., Eds.; Wiley: New York, 2002; p 185. (d) Chase, P. A.; Klein
Gebbink, R. J. M.; van Koten, G. J. Organomet. Chem. 2004, 689, 4016. (e)
Astruc, D.; Heuze, K.; Gatard, S.; Me´ry, D.; Nlate, S.; Plault, L. AdV. Synth.
Catal. 2005, 347, 329. (f) Me´ry, D.; Astruc, D. Coord. Chem. ReV. 2006, 250,
1965. (g) Helms, B.; Fre´chet, J. M. J. AdV. Synth. Catal. 2006, 348, 1125. (h)
Andre´s, R.; de Jesu´s, E.; Flores, J. C. New J. Chem. 2007, 31, 1161.
(9) (a) Wang, P.-W.; Liu, Y.-J.; Devadoss, C.; Bharati, P.; Moore, J. S. AdV.
Mater. 1996, 8, 237. (b) Sadamoto, R.; Tomioka, N.; Aida, T. J. Am. Chem.
Soc. 1996, 118, 3978. (c) Juris, A.; Balzani, V.; Barrigelletti, F.; Campagna, S.;
Denti, G.; Juris, A.; Serroni, S.; Venturi, M. Acc. Chem. Res. 1998, 31, 26. (d)
Kawa, M.; Fre´chet, J. M. J. Chem. Mater. 2001, 10, 286. (e) Andronov, A.;
Fre´chet, J. M. J. Chem. Commun. 2000, 1701. (f) Balzani, V.; Ceroni, P.; Juris,
A.; Venturi, M.; Campagna, S.; Puntoriero, F.; Serroni, S. Coord. Chem. ReV.
2001, 219-221, 545. (g) Daniel, M.-C.; Sakamoto, A.; Ruiz, J.; Astruc, D.;
Nishihara, H. Chem. Lett. 2006, 35, 38.
Agriculture leads to the production of many byproducts.
Hemicelluloses obtained from the straw of cereals enable one
to get low-cost molecules such as D-xylose and L-arabinose,
which can be valorized. After studies leading to the transforma-
tion of the above pentoses into products possessing surfactant
properties,1 we are now using them in dendrimer chemistry.2
(10) (a) Cameron, C. S.; Gorman, C. B. AdV. Funct. Mater. 2002, 12, 17.
(b) Daniel, M.-C.; Astruc, D. Chem. ReV. 2004, 104, 293. (c) Ong, W.; Grindstaff,
J.; Sobransingh, D.; Toba, R.; Quintela, J. M.; Peinador, C.; Kaifer, A. E. J. Am.
Chem. Soc. 2005, 127, 3353. (d) Astruc, D.; Ornelas, C.; Ruiz, J. J. Inorg.
Organomet. Polym. Mater. 2008, 18, 4. (e) Astruc, D.; Ornelas, C.; Ruiz, J.
Acc. Chem. Res. 2008, 41, 841.
† UMR CNRS No. 5255, Universite´ Bordeaux I.
‡ Universite´ Reims-Champagne-Ardenne.
§ UMR CNRS No. 5629, Universite´ Bordeaux 1.
10.1021/jo900554b CCC: $40.75 2009 American Chemical Society
Published on Web 05/22/2009
J. Org. Chem. 2009, 74, 5071–5074 5071