Synthesis of Kalasinamide, a Putative Plant Defense Phototoxin

The first total synthesis of the azaanthracene kalasinamide (1) is described, and the discrepancy in the reported C-13 NMR data and melting points for the natural product from two different sources is resolved. Kalasinamide is prone to autosensitized photooxidation, in solution and in the solid state, to give the corresponding quinone, marcanine A (8). This transformation may be representative of a novel and more general step in the biosynthesis of (aza)anthraquinones. Through its ability to generate toxic singlet oxygen, kalasinamide may serve a protective role, defending the plant against predation and the invasion of microbial pathogens, following mechanical insult.