2
962
A.M. Gellett et al. / Journal of Organometallic Chemistry 693 (2008) 2959–2962
pound 4 (749 mg, 73%). R
f
= 0.90 (acetone–hexanes 1:1). FT-IR
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(
(
neat): 3320, 3094, 2978, 1713, 1652, 1530, 1392, 1367, 1153,
[
À1
1
1
1
4
1
3
C
106 cm
3
. H NMR (CDCl ) d = 1.25–1.67 (m, 6H), 1.41 (s, 9H),
.43 (s, 9H), 3.14 (m, 2H), 3.27 (s, 2H), 4.10 (br, 5H), 4.12 (m,
1
3
3
H), 5.00 (d, 1H). C NMR (75 MHz, CDCl ) d = 171.8, 170.9,
(
b) P. Zanello, G. Opromolla, L. Pardi, K.H. Pannell, H.K. Sharma, Organomet.
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+
1.0, 29.0, 28.3, 28.0, 22.4. MS (FAB+) m/z [M+H] calcd for
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(
(
2006) 95;
27
40
H N
2
O
5
Fe: 528; found: 528.
b) C. Baldi, E. Licandro, S. Maiorana, D. Resemini, C. Rigamonti, L. Falciola, M.
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a
e
4
.3. General procedure for the synthesis of N -N -(ferrocene-1-
(
(
d) A.-S. Carlstrom, T. Frejd, J. Organomet. Chem. 55 (1990) 4175;
e) K. DiGleria, H.A.O. Hill, C.J. McNeil, Anal. Chem. 58 (1986) 1203.
acetyl)- -lysine (1)
L
[
6] (a) For extensive reviews see Ref 1and H.-B. Kraatz, J. Inorg. Organomet.
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a
e
N -(1,1-Dimethylethoxycarbonyl)-N -(ferrocene-1-acetyl)-
L
-ly-
(
b) H.-B. Kraatz, M. Galka, Metal Ions Biol. Syst. 38 (2001) 385.
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sine-tert-butyl ester (4, 269 mg, 0.51 mmol) and anisole (0.117 ml,
.07 mmol) were dissolved in dry CH Cl (2.5 ml) and cooled in an
[
1
2
2
5
ice bath. A 0.50 ml aliquot (6.49 mmol) of trifluoroacetic acid (TFA)
was slowly introduced into the flask and after stirring for 5 min,
the dark green mixture was warmed to room temperature. After
addition of another 0.80 ml (10.4 mmol) of TFA, the mixture was
stirred for 3–4 h. Excess TFA was removed under vacuum leaving
a thick, dark green residue that was applied to a flash silica gel col-
umn and washed with acetone–hexanes (6:4). The product was
eluted with 3% triethylamine in methanol and concentrated under
reduced pressure. The sample was further purified using reversed
phase chromatography on a solid phase extraction column with a
gradient of 10-25% acetonitrile in water. Fractions containing pure
product were detected by HPLC in 6:4 water–acetonitrile
(b) A. Hess, J. Sehnert, T. Weyhermuller, N. Metzler-Nolte, Inorg. Chem. 39
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[
[
(
2000) 229.
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(
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(
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[
[
(
(
b) Y. Dagani, A. Heller, J. Phys. Chem. 91 (1987) 1285;
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(
(
5
2
k = 225 nm) and lyophilized to yield 1 as a yellow-orange solid
96% pure, 159 mg, 84%). R = 0.47 [reverse phase TLC: CH CN-
0 mM sodium acetate pH 4.5 (4:6)]. IR (Nujol mull): 3300, 2871,
f
3
(d) K. DiGleria, H.A.O. Hill, L.L. Wong, FEBS Lett. 390 (1996) 142;
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À1
1
(f) M. Salmain, G. Jaouen, C.R. Chem. 6 (2003) 249.
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724, 1628, 1525, 1203, 1171, 1104 cm
6
. H NMR (DMSO-d )
[
d = 1.14–1.44 (m, 6H), 3.10 (m, 2H), 3.28 (br, 2H), 3.99 (s, 1H),
.08 (m, 5H), 4.12 (m, 4H), 7.48 (br, 1H), 7.85 (br, 1H). HPLC-MS
4
+
(
24 2 3
FAB+) m/z [M+H] calcd for C18H N O Fe: 373.3; found: 373.5.
(
b) S. Routier, H. Vezin, E. Lamour, J.-L. Bernier, J.P. Catteau, C. Bailly, Nucleic
4
.4. DNA cleavage experiments
Acid Res. 27 (1999) 4160.
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Sci. USA 87 (1990) 2882;
[
DNA cleavage assays (20
DNA (New England Biolabs, 75
centrations (0–150 M) of 1 or ferroceneacetic acid (Sigma) dis-
l
l) contained 1.0
lg of pUC19 vector
(
b) G.M. Heilek, H.F. Noller, Science 272 (1996) 1659;
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2 (1995) 1113;
lM bp) along with increasing con-
9
l
(
(
d) P.S. Pendergrast, Y.W. Ebright, R.H. Ebright, Science 265 (1994) 959;
e) D.P. Mack, B.L. Iverson, P.B. Dervan, J. Am. Chem. Soc. 110 (1988) 7572.
solved in 10% DMSO in 10 mM Tris–HCl, pH 8.0. After incubation
for 16 h at 25 °C, the cleavage products of each reaction were sepa-
rated by gel electrophoresis (1% agarose, 0.5 lg/ml ethidium bro-
(
b) K. Kowalski, N. Suwaki, J. Zakrzewski, A.J.P. White, N. Long, D.J. Mann,
mide) in 0.5 Â TBE buffer at 90 V for 90 min, visualized by UV
light, and captured on a digital image. The intensity of each band
was measured using ImageAide Band Matching software (Spectro-
nics Corporation) in order to calculate the percentage of each DNA
form generated during a reaction. An appropriate correction factor
was applied to compensate for the low affinity of supercoiled (SC)
DNA in comparison to the nicked circular (NC) and linear (L) forms
of DNA [26].
Dalton Trans. (2007) 743;
(c) H. Tamura, M. Miwa, Chem. Lett. (1997) 1177.
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[
[
(
b) J. Sehnert, A. Hess, N. Metzler-Nolte, J. Organomet. Chem. 349 (2001) 637.
[20] L. Barisic, V. Rapic, N. Metzler-Nolte, Eur. J. Inorg. Chem. (2006) 4019.
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(
(
1989) 182;
b) C.J. Noren, S.J. Anthony-Cahill, D.J. Suich, K. Noren, M.C. Griffith, P.G.
Schultz, Nucleic Acids Res. 18 (1989) 83.
[
[
22] S.A. Robertson, C.J. Noren, S.J. Anthony-Cahill, M.C. Griffith, P.G. Schultz,
Nucleic Acids Res. 17 (1989) 9649.
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Acknowledgements
65 (1991) 537.
The authors wish to thank Drs. Marvin J. Miller and Lester J.
Lambert for helpful discussions and gratefully acknowledge finan-
cial support by an award to Dickinson College from the Howard
Hughes Medical Institute under the Undergraduate Biological
Science Education Program and also by the National Institutes of
Health (Grant GM38200 to P.W. H.).
[24] L.M. Schnaith, R.S. Hanson, L. Que Jr., Proc. Natl. Acad. Sci. USA 91 (1994) 569.
[
[
25] T.A. van den Berg, B.L. Feringa, G. Roelfes, Chem. Commun. (2007) 180.
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