The Synthesis and Chemistry of A Simplified, Functional Analogue of Neocarzinostatin Chromophore: Identification of an Intramolecular 1,5-Hydrogen Atom Transfer Relevant to the Mechanism and Cleavage Selectivity of Diyl-Based DNA Cleaving Agents

Article abstract of DOI:10.1016/S0040-4020(01)80627-X

The synthesis and chemistry of a monocyclic analogue of neocarzinostatin chromophore are described.This analogue is activated through a Michael addition process and provides cycloaromatized products similar to those obtained in the activation of neocarzinostatin chromophore.Mechanistic studies on this analogue have led to the first identification of a diyl self-quenching pathway based on a 1,5-hydrogen atom transfer that provides a novel hypothesis about the relationship between thiol structure and DNA single and double strand cleavage selectivity for neocarzinostatin chromophore and diyl-based cleaving agents.