Phthalimide hydroperoxides as efficient photochemical hydroxyl radical generators. A novel DNA-cleaving agent
Phthalimide hydroperoxides as efficient photochemical hydroxyl radical generators. A novel DNA-cleaving agent
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DOI：
10.1021/ja00158a067
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发表时间：
1990
影响因子：
15
通讯作者：
I. Saito;M. Takayama;T. Matsuura;S. Matsugo;S. Kawanishi
中科院分区：
文献类型：
--
作者：
I. Saito;M. Takayama;T. Matsuura;S. Matsugo;S. Kawanishi
While a variety of methods for the generation of hydroxyl radical are known, 1the use of organic hydroperoxides as a hydroxyl radical source has not been fully realized. 2, 3 Hydroperoxides that can efficiently generate hydroxyl radical by photoirradiation with long-wavelength light (> 300 nm) without using metal ions would be an extremely useful hydroxyl radical source, particularly for the design of DNA-cleaving molecules. 3 Wereport herein an efficient method for generating hydroxyl radicalby irradiation (> 300 nm) of hydroperoxides derived from phthalimides, which may be widely used as a convenient and clean hydroxyl radical source. We also disclose their use as an effective photochemicalDNA cleaver. Our strategy for generating hydroxyl radical is based on the photochemical 7-hydrogen abstraction of phthalimide6 and the earlier finding7* that the hydroperoxyalkyl radicals such as 1 un-dergo extremely facile 0-cleavage of the labile 0-0 bond giving rise to hydroxyl radical as illustrated in Scheme I. Since y-hydroperoxy ketones normally exist in a cyclic peroxide form, we have chosen hydroperoxides derived from phthalimides as the precursor. Hydroperoxides 2 and 3 are readily available by singlet oxygenation of 4 in a 1: 1 ratio, whereas 5 and 6 were prepared from the corresponding dimethyl ketals (ethereal H202/cat.
