March 2010
407
and N-succinimidyl 4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate (5) of Education, Culture, Sports, Science and Technology Grant-in-Aid for Sci-
(6.5 mg, 0.020 mmol) were reacted by the same procedure described above entific Research on a Priority Area, 18032007, for Scientific Research on In-
to afford 8 (7.8 mg, 0.014 mmol, 69%) as a colorless amorphous mass.
1H-NMR (DMF-d7) d: 7.93 (2H, d, Jꢂ8.0 Hz), 7.35 (2H, d, Jꢂ8.0 Hz),
3.65 (2H, m), 3.10 (1H, m), 2.74 (1H, m), 2.55 (1H, m), 13C-NMR (DMF-
novative Areas, 20200038 and for Scientific Research (C), 19510210,
21510219.
d7) d: 166.0, 143.0, 131.7, 129.0, 123.9 (q, 1JCFꢂ273.5 Hz), 123.5, 61.0, References
52.0 40.5, 29.7 (q, 2JCFꢂ40.0 Hz), 19F-NMR (DMF-d7) d: ꢃ66.8, 195Pt-
NMR (DMF-d7) d: ꢃ2270.
1) Hatanaka Y., Nakayama H., Kanaoka Y., Rev. Heteroatom Chem., 14,
213—243 (1996).
(N1-[4-[3-(Trifluoromethyl)-3H-diazirin-3-yl]-2-methoxybenzoyl]-
propane-1,2,3-triamine)dichloroplatinum(II) (9) Compound 3 (9.2 mg,
0.020 mmol) and N-succinimidyl 5-[(3-(trifluoromethyl)-3H-diazirin-3-yl]
2-methoxybenzoate (6) (6.4 mg, 0.018 mmol) were reacted by the same pro-
cedure described above to afford 9 (7.5 mg, 0.013 mmol, 70%) as a colorless
amorphous mass.
2) Gillingham A. K., Koumanov F., Hashimoto M., Holman G. D., “De-
tection and Analysis of Glucose Transporters Using Photolabelling
Techniques in Membrane Transport: A Practical Approach,” ed. by
Baldwin S. A., Oxford University Press, Oxford, 2000, pp. 193—207.
3) Tomohiro T., Hashimoto M., Hatanaka Y., Chem. Record, 5, 385—395
(2005).
1H-NMR (DMF-d7) d: 8.65 (1H, s), 7.80 (1H, d, Jꢂ8.0 Hz), 7.35 (1H, d,
Jꢂ8.0 Hz), 3.78 (2H, m), 3.15 (1H, m), 2.74 (1H, m), 2.55 (1H, m), 13C-
NMR (DMF-d7) d: 165.4, 159.5, 131.7, 129.9, 124.1 (q, 1JCFꢂ273.5 Hz),
121.9, 120.5, 114.0, 61.1, 56.9, 51.7, 40.0, 29.6 (q, 2JCFꢂ40.4 Hz), 19F-NMR
(DMF-d7) d: ꢃ67.3, 195Pt-NMR (DMF-d7) d: ꢃ2275.
Photolysis of the Diazirinyl Compounds 8 and 9 A methanolic solu-
tion of 8 and 9 (56 mM) was placed in a quartz cuvette. After replacing the
inner atmosphere with nitrogen and cooling on ice, photolysis was carried
out using a 15 W black light (UVP, San Gabriel, California, U.S.A.) at a dis-
tance of 2 cm from the surface of the light source. The UV spectrum was
measured at the intervals indicated in Fig. 1. The half-life was calculated
from a semi-log plot of the decay of the absorbance at 360 nm. After meas-
urement of absorbance, the irradiated sample was concentrated. The residue
was re-dissolved in CD3OD and subjected to 19F-NMR analysis.
4) Hashimoto M., Hatanaka Y., Eur. J. Org. Chem., 2008, 2513—2523
(2008).
5) Heetebrij R. J., Talman E. G., van Velzen M. A., van Gijlswijk R. P.
M., Snoeijers S. S., Schalk M., Wiegant J., van de Rijke F., Kerkhoven
R. M., Raap A. K., Tanke H. J., Reedijk J., Houthoff H. J., Chem-
BioChem, 4, 573—583 (2003).
6) Guggenheim E. R., Xu D., Zhang C. X., Chang P. V., Lippard S. J.,
ChemBioChem, 10, 141—157 (2009).
7) Sadler P. J., ChemBioChem, 10, 73—74 (2009).
8) Guggenheim E. R., Ondrus A. E., Movassaghi M., Lippard S. J.,
Bioorg. Med. Chem., 16, 10121—10128 (2008).
9) Zhang C. X., Chang P. V., Lippard S. J., J. Am. Chem. Soc., 126,
6536—6537 (2004).
10) Benoist E., Loussouarn A., Remaud P., Chatal J.-F., Gestin J.-F., Syn-
thesis, 8, 1113—1118 (1998).
11) Molenaar C., Teuben J.-M., Heetebrij R. J., Tanke H. J., Reedijk J., J.
Biol. Inorg. Chem., 5, 655—665 (2000).
12) Nassal M., Liebigs Ann. Chem., 1510—1523 (1983).
Reactivities of Synthetic Compounds towards GMP Complex forma-
tion between organo-platinum compounds with or without irradiation and
GMP were performed at a 5.0 mM GMP and 2.5 mM synthetic compounds in
a deuterated 50 mM sodium phosphate buffer pH 7.0 at 50 °C. DMF-d7 was
used to dissolve the organo-platinum compounds. Reaction mixture was 13) Hatanaka Y., Hashimoto M., Hidari K. I.-P. J., Sanai Y., Nagai Y.,
subjected to 1H-NMR spectroscopy analysis directly. The H-8 proton of
Kanaoka Y., Bioorg. Med. Chem. Lett., 5, 2859—2862 (1995).
guanosine base was drastically downfield shift before (8.16 ppm) and after 14) Hashimoto M., Hatanaka Y., Anal. Biochem., 348, 154—156 (2006).
(8.52 ppm) coordination platinum to guanosine. Calculations were per-
formed by relative integration of the H8 proton signals of both reaction
product and starting material during the reaction.
15) Hosoya T., Hiramatsu T., Ikemoto T., Nakanishi M., Aoyama H.,
Hosoya A., Iwata T., Maruyama K., Endo M., Suzuki M., Org. Biomol.
Chem., 2, 637—641 (2004).
16) Hashimoto M., Hatanaka Y., Sadakane Y., Nabeta K., Bioorg. Med.
Chem. Lett., 12, 2507—2510 (2002).
Acknowledgements This research was partially supported by Ministry