M. Kueny-Stotz et al. / Tetrahedron Letters 52 (2011) 2906–2909
2909
Scheme 4. Final steps to dye-derivatized dendron 2. Reagents and conditions: (k) Boc2O (1.0 equiv), CH2Cl2, 0 °C?rt, one night, 86%; (l) pTsCl (1.1 equiv), NEt3 (2.3 equiv),
CH2Cl2, 0 °C?rt, 40 h, 93%; (m) 3 (1.0 equiv), 20 (1.0 equiv), K2CO3 (4.0 equiv), KI (0.3 equiv), acetone, 60 °C, 48 h, 95%; (n) TFA (15.0 equiv), CH2Cl2, 0 °C?rt, one night, 97%;
(o) POCl3 (20.0 equiv), rt, 72 h; (p) 22 (1.0 equiv), 23 (1.0 equiv), NEt3 (3.0 equiv), 4-DMAP (0.1 equiv), CH2Cl2/DMF 4:1, 0 °C?rt, one night, 54% (steps n + o); (q) TMSBr
(15.0 equiv), CH2Cl2, 0 °C?rt, one night, 95%.
S. Chem. Mater. 2008, 20, 5869–5875; (d) Boyer, C.; Bulmus, V.; Priyanto, P.;
Teoh, W. Y.; Amal, R.; Davis, T. P. J. Mater. Chem. 2009, 19, 111–123.
Acknowledgments
11. Freeman, A. W.; Chrisstoffels, L. A. J.; Fréchet, J. M. J. J. Org. Chem. 2000, 65,
We would like to thank Emilie Voirin and Emilie Couzigné for
their assistance. We also thank the European Community for fund-
ing through the NANOMAGDYE project CP-FP 214032-2 and Dr.
Geneviève Pourroy, coordinator of the NANOMAGDYE project.
7612–7617.
12. Snow, A. W.; Foos, E. E. Synthesis 2003, 35, 509–512.
13. Bouzide, A.; Sauvé, G. Org. Lett. 2002, 4, 2329–2332.
14. Compound 1: to a solution of 12 (250 mg, 0.25 mmol) in 15 mL of CH2Cl2 at
0 °C, is added dropwise 500 lL (3.75 mmol, 15.0 equiv) of TMSBr. After one
night stirring at room temperature, the volatiles are evaporated and methanol
is added to the crude product and evaporated several times. Compound 1 is
obtained as a dark yellow oil in 93% yield without further purification. 1H NMR
(300 MHz, CD3OD, 20 °C): d (ppm) = 3.08 (d, 2H, 2J = 21.5 Hz), 3.34 (s, 6H),
3.50–3.77 (m, 52H), 3.78 (t, 2H, 3J = 5.2 Hz), 3.84 (t, 4H, 3J = 5.2 Hz), 4.09–4.17
Supplementary data
Supplementary data (synthetic procedures, characterization
and 1H and 13C NMR spectra for compounds 1, 2, 3, 12, 21, 22,
and 24) associated with this article can be found, in the online ver-
(m, 6H), 6.64 (d, 2H, 4J = 2.5 Hz). 13C NMR (75 MHz, CD3OD, 20 °C):
d
(ppm) = 35.61 (1JCP = 135.5 Hz), 59.07, 62.16, 69.93, 70.76, 71.26, 71.30,
71.46, 71.56, 71.66, 72.88, 73.43, 73.56, 110.38 (3JCP = 5.8 Hz), 129.64
(2JCP = 9.1 Hz), 138.15 (5JCP = 2.5 Hz), 153.65 (4JCP = 2.5 Hz). 31P NMR (81 MHz,
CD3OD, 20 °C): d (ppm) = 24.32. MALDI: calculated for C41H78O22P: 953.47,
obtained: 953.47; calculated for
C41H77NaO22P: 975.45, obtained: 975.46;
References and notes
calculated for
C41H77KO22P: 991.43, obtained: 991.43; calculated for
C41H76Na2O22P: 997.44, obtained: 997.44. IR (KBr, cmꢀ1): 3409, 2875, 1590,
1511, 1443, 1352, 1249, 1106, 955, 848.
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C.; Kung, S.-H.; Kim, M.; Peng, X.; El-Aama, R.; Rühl, E. Synthesis 2010, 42, 1150–
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Rühl, E.; Graf, C. J. Mater. Chem. 2010, 20, 7842–7853.
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Perriat, P.; Billotey, C.; Taleb, J.; Pourroy, G.; Begin-Colin, S. Chem. Commun.
2010, 46, 985–987; (c) Basly, B.; Felder-Flesch, D.; Perriat, P.; Pourroy, G.;
10. (a) Daou, T. J.; Buathong, S.; Ung, D.; Donnio, B.; Pourroy, G.; Guillon, D.; Bégin,
15. (a) Walker, P. M.; Hussain, M.; Humphrey, C. S. Breast 2002, 11, 343–345; (b)
Patel, A.; Pain, S. J.; Britton, P.; Sinnatamby, R.; Warren, R.; Bobrow, L.; Barber,
R. W.; Peters, A. M.; Purushotham, A. D. Eur. J. Surg. Oncol. 2004, 30, 918–923;
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17. Compound 2: to a solution of 24 (136 mg, 0.10 mmol) in 6 mL of CH2Cl2 at 0 °C,
is added dropwise 200 lL (1.50 mmol, 15.0 equiv) of TMSBr. After one night
stirring at room temperature, the volatiles are evaporated and methanol is
added to the crude product and evaporated several times. Compound 2 is
obtained as a dark blue oil in 95% yield without further purification.1H NMR
(300 MHz, DMSO-d6, 20 °C): d (ppm) = 1.20 (t, 3J = 6.7 Hz, 12H), 2.78 (d, 2H,
2J = 21.0 Hz), 3.00 (bt, 2H, 3J = 5.8 Hz), 3.22 (s, 6H), 3.39–3.71 (m, 50H), 3.93 (bt,
3
2H, J = 5.2 Hz), 4.00–4.07 (m, 4H), 6.57 (s, 2H), 6.98 (m, 4H, AA0 part of an
3
AA0BB0 system), 7.23 (d, 1H, J = 8.1 Hz), 7.27 (m, 4H, BB0 part of an AA0BB0
system), 7.85 (dd, 1H, 3J = 8.1 Hz, 4J = 1.8 Hz), 8.03 (br s, 1H), 8.35 (d, 1H,
4J = 1.8 Hz). 13C NMR (75 MHz, DMSO-d6, 20 °C):
d (ppm) = 12.70, 35.29
(1JCP = 132.7 Hz), 42.42, 45.26, 58.02, 60.19, 68.32, 68.97, 69.12, 69.56, 69.69,
69.76, 69.81, 69.94, 71.25, 71.77, 72.30, 108.98 (3JCP = 5.8 Hz), 113.27, 125.84,
125.97, 126.08, 129.46 (2JCP = 8.5 Hz), 131.68, 136.01 (5JCP = 3.4 Hz), 139.80,
139.99, 141.38, 148.22, 151.66 (4JCP = 2.2 Hz), 154.53, 173.61. 31P NMR
(81 MHz, DMSO-d6, 20 °C):
d
(ppm) = 18.29. MALDI: calculated for
obtained: 1302.57; calculated for
60H92N3NaO22PS2: 1324.53, obtained: 1324.55. IR (KBr, cmꢀ1): 3416, 2925,
C60H93N3O22PS2:
1302.54,
C
S. Sens. Actuators,
B 2007, 126, 159–162; (b) Daou, T. J.; Begin-Colin, S.;
2868, 1613, 1579, 1409, 1341, 1251, 1193, 1109, 1018, 934, 830, 705, 609. UV/
Vis (in H2O): kmax ) = 646 (82 800) nm (shoulder around 600 nm).
Greneche, J. M.; Thomas, F.; Derory, A.; Bernhardt, P.; Legaré, P.; Pourroy, G.
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(e