4. C1′-Radical Generation, Reactivity and Related Mechanistic Implications

4.1. C1′-Radical Formation

Abstraction of the C1′-hydrogen atom in duplex DNA by diffusible species (eg HO•) is limited by its position in the minor groove (Fig. 1A), despite the relatively modest C1′-H BDE (Table 1). The solvent inaccessibility of the C1′-hydrogen is overcome by DNA oxidizing agents that bind in the minor groove. For instance, the antitumor agent neocarzinostatin (NCS), which forms a biradical upon reductive activation in the minor groove abstracts hydrogen atoms from the C1′-position.47 Activated forms of some coordination compounds, such as manganese porphyrins (MnPy) and copper bis-phenanthroline (Cu•OP2) also abstract the C1′-hydrogen atom.4850
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