1562
X.-M. Meng et al. / Tetrahedron Letters 47 (2006) 1559–1562
previous sensors in the applications where Co2+, Ni2+
Cu2+, or Cd2+ coexists with Zn2+
,
yama, S.; Kikuchi, K.; Hirano, T.; Urano, Y.; Nagano, T.
J. Am. Chem. Soc. 2002, 124, 10650–10651; (d) Hirano, T.;
Kikuchi, K.; Urano, Y.; Nagano, T. J. Am. Chem. Soc.
2002, 124, 6555–6562; (e) Woodroofe, C. C.; Lippard, S. J.
J. Am. Chem. Soc. 2003, 125, 11458–11459; (f) Chang, C.
J.; Jaworski, J.; Nolan, E. M.; Sheng, M.; Lippard, S. J.
Proc. Natl. Acad. Sci. U.S.A. 2003, 101, 1129–1134; (g)
Sensi, S. L.; Ton-That, D.; Weiss, J. H.; Rothe, A.; Gee,
K. R. Cell Calcium 2003, 34, 281–284.
.
In conclusion, we have designed, synthesized, and char-
acterized two novel fluorescent chemosensors that are
highly sensitive to Zn2+. The synthesis of these two
Zn2+ sensors was accomplished in four steps from inex-
pensive starting materials. The two new sensors showed
much better selectivity to many other metal ions as com-
pared to the previously reported Zn2+ sensors. Thus, the
two new sensors reported here add novel tools to the
arsenal of Zn2+ detection and imaging. Furthermore,
the present study has confirmed Urano’s very recent
finding that the carboxylic group plays almost no role
in the fluorescence properties of the fluorescein
molecule.5
5. Urano, Y.; Kamiya, M.; Kanda, K.; Ueno, T.; Hirose, K.;
Nagano, T. J. Am. Chem. Soc. 2005, 127, 4888–4894.
6. Characterization of 3: 1H NMR (DMSO-d6): d 1.23 (6H, t,
J = 7.2 Hz), 4.17 (4H, q, J = 7.2 Hz), 4.32 (4H, s), 6.58–
6.66 (4H, m), 6.77 (2H, d, J = 8.8 Hz), 7.22 (2H, d,
J = 8.8 Hz), 7.28 (1H, s), 7.31 (1H, s). 13C NMR (DMSO-
d6): d 14.3, 53.5, 61.4, 95.6, 104.8, 108.0, 110.2, 114.2,
117.4, 126.5, 128.5, 129.3, 130.1, 148.7, 149.5, 155.2, 157.3,
158.4, 159.6, 169.6, 185.8. HRMS (ESI): 476.1792 (calcd
for C27H26NO7 MH+: 476.1748).
7. Characterization of 4: 1H NMR (DMSO-d6): d 1.21 (6H, t,
J = 7.2 Hz), 4.15 (4H, q, J = 7.2 Hz), 4.33 (4H, s), 6.74–
6.76 (2H, m), 6.83 (2H, d, J = 8.5 Hz), 7.28 (1H, s), 7.33
(2H, d, J = 8.6 Hz), 7.39 (1H, s). 13C NMR (DMSO-d6): d
14.3, 53.3, 61.4, 96.7, 106.3, 109.5, 117.4, 119.3, 123.7,
127.3, 129.2, 130.0, 133.1, 148.8, 149.6, 155.6, 157.8, 159.1,
160.3, 169.7, 178.8. HRMS (ESI): 544.0935 (calcd for
C27H24Cl2NO7 MH+: 544.0927).
Acknowledgements
This research was supported by the NSFC (Nos.
20332020, 20472079).
References and notes
1
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6.27–6.32 (2H, m), 6.52 (2H, d, J = 8.7 Hz), 6.67–6.71
(2H, m), 7.06 (2H, d, J = 8.7 Hz), 7.25 (1H, s), 7.27 (1H,
s). 13C NMR (D2O): d 51.4, 104.3, 104.4, 110.3, 113.6,
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1
9. Characterizations for 2: H NMR (D2O): d 4.07 (4H, s),
6.65–6.68 (2H, m), 6.70 (2H, d, J = 8.4 Hz), 7.28 (2H, d,
J = 8.5 Hz), 7.40 (1H, s) 7.65 (1H, s). 13C NMR (D2O): d
55.9, 104.3, 104.4, 111.4, 111.9, 112.8, 119.6, 127.8, 129.4,
129.8, 131.8, 131.9, 150.4, 157.0, 157.1, 157.3, 160.7, 174.2,
179.0.
HRMS
(ESI):
488.0309
(calcd
for
C23H16Cl2NO7MH+: 488.0305).
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