7120
L. Moreau et al. / Tetrahedron Letters 47 (2006) 7117–7120
supramolecular systems. The formation of actinide
loaded microspheres illustrates that fluorocarbon nucleo-
amphiphiles can be used to construct hybrid supramo-
lecular systems. Such materials are likely to be of
interest for multiple applications ranging from chemis-
try to medicine. In fine, these data show that combin-
ing fluorocarbon chains with nucleoside moieties affords
interesting structures and these results broaden the
scope and potential uses of nucleoamphiphiles in the
field of supramolecular chemistry.
9. Moreau, L.; Barth e´ l e´ my, P.; El Maataoui, M.; Grinstaff,
M. W. J. Am. Chem. Soc. 2004, 126, 7533.
0
0
1
0. Preparation of 2 ,3 -O-di-2H,2H,3H,3H-perfluoro-undeca-
0
noyl-uridine-5 -phosphocholine 5: 2H,2H,3H,3H-perfluo-
roundecanoic acid 2 (720 mg, 3 equiv, 1.47 mM), DCC
(
1
(
2
303 mg, 3 equiv, 1.47 mM) and DMAP (180 mg, 3 equiv,
.47 mM), were added to uridine phosphocholine 4
200 mg, 0.49 mM) in 12 mL of anhydrous DMF. After
4 h at room temperature, the DMF was evaporated and
1
7
the residual solid was dissolved in 20 mL of methylene
chloride–methanol 1:1. DCU was removed by filtration
and solvent was removed under reduced pressure. The
crude material was purified by exclusion chromatography
(
(
LH 20, DCM/MeOH 5/5). 280 mg of a white powder
Acknowledgements
product 5) was isolated. (Yield: 42%.) rf: 0.30 (reverse
1
phase, DCM/MeOH 5/5).
CD
–
CH
H
NMR (300.13 MHz,
CH –), 3.64 (m, 4H,
CO CH –), 4.23 (s, 9H, N(CH3)3), 4.65 (m, 2H,
This work was supported by the Army Research Office
and the ‘Association pour la Recherche sur le Cancer’
ARC), which are greatly acknowledged.
3
OD) d: 2.31 (m, 4H, –CF
2
2
2
2
(
+
0
2
N ), 5.09 (m, 2H, H5 ), 5.28 (m, 2H, CH
2
O), 5.40
0
0
0
(
(
m, 1H, H4 ), 6.47 (m, 1H, H3 ), 6.58 (m, 1H, H2 ), 6.79
d, J = 8.12 Hz, 1H, H5), 7.14 (d, J = 6.61 Hz, 1H, H1 ),
0
1
3
References and notes
8.90 (d, J = 8.12 Hz, 1H, H6). C NMR (75.468 MHz,
CD OD) d: 26.03 (–C@OCH –), 26.99 (–C@OCH –),
31.91 (–CF CH –), 33.22 (–CF
60.64 (CH O), 66.13 (C ), 67.58 (N CH
74.97 (C ), 83.12 (C ), 87.89 (C ), 103.93 (C
(–CF2ꢀ), 107.68 (–CF –), 108.05 (–CF –), 108.15 (–CF
111.60 (–CF –), 112.17 (–CF ), 112.67 (–CF –), 116.62
(–CF –), 142.30 (C ), 152.40 (C ), 165.82 (C ), 171.73
(–C@O–), 171.94 (–C@O–). NMR (282 MHz,
CD ), ꢀ82.94 (t,
OD): ꢀ82.81 (t, J = 10.31 Hz, 3F, CF
J = 10.31 Hz, 3F, CF ), ꢀ123.38
), ꢀ116.25 (m, 4F, CF
(m, 12F, CF ), ꢀ124.92 (m, 4F,
), ꢀ124.22 (m, 4F, CF
CF ). P NMR (121.495 MHz,
), ꢀ127.78 (m, 4F, CF
CD
3
2
2
+
1
2
3
. Riess, J. G. Tetrahedron 2002, 58, 4113.
2
2
2 2 3 3
CH –), 54.78 N (CH ) ,
+
. Krafft, M. P. Adv. Drug Delivery Rev. 2001, 47, 209.
. (a) Kissa, E. Fluorinated Surfactants. Synthesis. Proper-
ties. Applications. In Surfactant Science Series; Marcel
Dekker: New York, 1994; Vol. 50; (b) Kissa, E. Fluori-
nated surfactants and repellents, 2nd ed. In Surfactant
science; Marcel Dekker: New York, 2001.
. Barth e´ l e´ my, P.; Chaudier, Y.; Tomao, V.; Pucci, B.
Fluorocarbon amphiphiles for supramolecular assemblies.
In Self Assembly; Robinson, B. H., Ed.; IOS Press:
Amsterdam, The Netherlands, 2003; pp 80–91.
. (a) Shchukin, D. G.; Sukhorukov, G. B.; M o¨ hwald, H.
Angew. Chem., Int. Ed. 2003, 42, 4472; (b) McKenna, B. J.;
Birkedal, H.; Barti, M. H.; Deming, T. J.; Stucky, G. D.
Angew. Chem., Int. Ed. 2004, 43, 5652; (c) Thibault, R. J.;
Hotchkiss, P. J.; Gray, M.; Rotello, V. M. J. Am. Chem.
Soc. 2003, 125, 11249; (d) Peyratout, C. S.; D a¨ hne, L.
Angew. Chem., Int. Ed. 2004, 43, 3762; (e) Webb, A. G.;
Wong, M.; Kolbeck, K. J.; Magin, R.; Suslick, K. S.
J. Magn. Reson. Imaging 1996, 6, 675.
. (a) Berti, D.; Baglioni, P.; Bonaccio, S.; Barsacchi-Bo, G.;
Luisi, P. L. J. Phys. Chem. B 1998, 102, 303; (b) Onda, M.;
Yoshihara, K.; Koyano, H.; Ariga, K.; Kunitake, T.
J. Am. Chem. Soc. 1996, 118, 8524; (c) Baglioni, P.; Berti,
D. Curr. Opin. Colloid Interface Sci. 2003, 8, 55; Moreau,
L.; Grinstaff, M. W.; Barth e´ l e´ my, P. Tetrahedron Lett.
2
5
0
2
), 73.08 (C
), 106.25
–),
3
0
),
0
0
0
2
4
1
5
2
2
2
2
3
2
2
6
2
4
1
9
F
4
3
3
3
2
2
2
3
1
2
2
+
+
5
3
OD): ꢀ0.557 ppm. FAB MS (MH ): 1358.
11. (a) Ravily, V.; Santaella, C.; Vierling, P.; Gulik, A.
Biochim. Biophys. Acta (BBA) – Biomembranes 1997,
1324, 1; (b) Kunitake, T. Angew. Chem., Int. Ed. Engl.
1992, 31, 6, 709.
12. Santaella, C.; Vierling, P.; Riess, J. G.; Gulik-Krzywicki,
T.; Gulik, A.; Monasse, B. Biochim. Biophys. Acta (BBA)
– Biomembranes 1994, 1190, 25.
13. (a) Tiddy, G. J. T. Concentrated surfactant systems. In
Modern Trends of Colloid Science in Chemistry and
Biology; Eicke, H. F., Ed.; Birkh a¨ user: Basel, 1985; pp
148–159; (b) Smart, B. E. Characteristics of C–F systems.
In Organofluorine Chemistry: Principles and Commercial
Applications; Banks, R. E., Smart, B. E., Tatlow, J. C.,
Eds.; Plenum: New York, 1994; pp 57–88.
6
2
005, 46, 1593.
14. Schlosser, M.; Michel, D. Tetrahedron 1996, 52, 99.
15. Mukerjee, P. Coll. Surf., A 1994, 84, 1.
7
. Moreau, L.; Ziarelli, F.; Grinstaff, M. W.; Barth e´ l e´ my, P.
Chem. Commun. 2006, 15, 1661.
16. Ravey, J. C.; St e´ b e´ , M. Coll. Surf., A 1994, 84, 11.
17. (a) Bunzli, J.-C.; Piguet, C. Chem. Rev. 2002, 102, 1897;
(b) Hainfeld, J. F. Proc. Natl. Acad. Sci. U.S.A. 1992, 89,
11064; Gorden, A. E. V.; Xu, J.; Raymond, K. N.;
Durbin, P. Chem. Rev. 2003, 103, 4207.
8
. Compound
2 showed consisting spectroscopic data
according to the literature (Benno Hungerhoff, Helmut
Sonnenschein and Fritz Theil, J. Org. Chem. 2002, 67,
1781).