1002
F. Havas et al. / Tetrahedron Letters 48 (2007) 999–1002
13. A solution of n-BuLi (1.5 M in hexane, 1.1 equiv) was
slowly added to a stirred solution of 1.02 g (5.93 mmol,
1 equiv) of bromopicoline 6 in 10 mL of anhydrous THF
at ꢀ78 ꢁC, and the resulting mixture was stirred for 15 min
at this temperature. Then, a 0.44 M solution of anhydrous
ZnCl2 (1.1 equiv) in THF was added, and the stirring was
continued for 30 min at room temperature. In a separate
flask, a solution of 715 mg (3.85 mmol) of 7 in 5 mL of
anhydrous THF was added to a solution containing
5 mol % of a catalyst prepared by reaction of a 0.014 M
solution of Cl2Pd–(PPh3)2 with 2 equiv of diisobutylalu-
minium hydride (1.0 M in hexane) and the mixture was
stirred at room temperature for 10 min. The pyridylzinc
chloride solution prepared above was then added drop-
wise, and the resulting mixture was heated at reflux for
1.5 h, cooled, and poured into saturated aqueous
NaHCO3. The aqueous phase was extracted with Et2O
and the organic extracts were concentrated to give a solid
residue which was purified by flash chromatography over
alumina (petroleum ether/ether 90:10), to yield 827 mg
(84%) of compound 1 as a white solid. Mp: 122–123 ꢁC
(lit.14 116–117 ꢁC). IR (KBr pellet): m 1733 (C@O). 1H
NMR (CDCl3, 300 MHz): d 2.64 (s, 3H), 2.69 (s, 3H), 3.97
(s, 3H), 7.18 (d, 1H, J = 7.8 Hz), 7.69 (t, 1H, J = 7.8 Hz),
7.71 (s, 1H), 8.19 (d, 1H, J = 7.8 Hz), 8.71 (s, 1H). MS
(DCI/NH3): m/z = 243 [MH+, 100%].
Vander Elst, and Dr. S. Laurent (NMR and Molecular
Imaging Laboratory, University of Mons-Hainaut,
Belgium) for the determination of NMR relaxation
measurements.
References and notes
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2002, 82, 233–250; (b) Weibel, N.; Charbonniere, L. J.;
19. Selected data for compounds 2, 3, and [4ÆNa]Br. Compound
2: pale grey solid. Mp ꢁ180 ꢁC (dec.). IR (KBr pellet): m
Guardigli, M.; Roda, A.; Ziessel, R. J. Am. Chem. Soc.
2004, 126, 4888–4896.
1
1728, 1685 (C@O). H NMR (CD3OD, 300 MHz): d 3.58
6. Bifunctional chelators (BFCs) are ligands that bear one
end which is used to covalently attach the ligand to
biological material and one end which strongly coordinates
to the metallic ion; see for example: Woods, M.; Kovacs,
Z.; Sherry, A. D. J. Supramol. Chem. 2002, 2, 1–15.
7. (a) Picard, C.; Geum, N.; Nasso, I.; Mestre, B.; Tisnes, P.;
Laurent, S.; Muller, R. N.; Vander Elst, L. Bioorg. Med.
Chem. Lett. 2006, 16, 5309–5312; (b) Nasso, I.; Galaup,
(s br, 8H), 4.06 (s, 3H), 4.20 (s br, 2H), 4.26 (s br, 2H), 7.61
(d, J = 7.2 Hz, 1H), 8.08 (s, 1H), 8.15 (t, J = 7.2 Hz, 1H),
8.41 (d, J = 7.2 Hz, 1H), 8.74 (s, 1H). HRMS-FAB+ calcd
for [M+H]+ (C22H25N4O10) 505.15707, found 505.15742.
Compound 3: pale grey solid. Mp > 280 ꢁC (dec.). IR
(KBr pellet): m 1728, 1685 (C@O). 1H NMR (CD3OD,
300 MHz): d 2.55 (br m, 2H), 2.87 (br m, 4H), 3.10
(m, 2H), 3.39 (m, 2H), 3.60 (m, 2H), 3.90 (m, 2H), 4.07
(s+m, 5H), 4.30 (m, 2H), 7.64 (d, J = 8.1 Hz, 1H), 8.09
(s, 1H), 8.20 (t, J = 7.5 Hz, 1H), 8.47 (d, J = 8.1 Hz, 1H),
8.79 (s, 1H). HRMS-FAB+ calcd for [M+H]+
(C24H30N5O8) 516.20944, found 516.20965. Compound
[4ÆNa]Br complex: yellow solid. Mp ꢁ280 ꢁC (dec.). IR
(KBr pellet): m 1728 (C@O). 1H NMR (CDCl3, 300 MHz):
d 3.81 (br s, 10H); 3.91 (br s, 2H); 3.95 (s, 3H); 7.28
(m, 4H); 7.77–7.94 (m, 12H); 8.35 (s, 1H). HRMS-FAB+
calcd for [M+Na]+ (C38H32N8O2Na) 655.25459, found
655.25382. Anal. Calcd for C38H32N8O2NaBrÆ2H2O: C,
59.15; H, 4.70; N, 14.52. Found: C, 58.82; H, 4.89; N,
14.28.
`
C.; Havas, F.; Tisnes, P.; Picard, C.; Laurent, S.; Vander
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20. The number of coordinated water molecules (q) was
calculated from the following equation in which sH and sD
are the lifetimes (in ms) of the europium complex in H2O
and D2O, respectively: q = 1.2(1/sHꢀ1/sDꢀ0.25). Beeby,
A.; Clarkson, I. M.; Dickins, R. S.; Faulkner, S.; Parker,
D.; Royle, L.; de Sousa, A. S.; Williams, J. A. G.; Woods,
M. J. Chem. Soc., Perkin Trans. 2 1999, 493–503.
1988, 53, 918–920; Fuerstner-type coupling: (c) Furstner,
¨
´
A.; Leitner, A.; Mendez, M.; Krause, H. J. Am. Chem.
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Negishi, E. Acc. Chem. Res. 1982, 15, 340–348.
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