Disclosing biosynthetic connections and functions of atypical angucyclinones with a fragmented C-ring

This review on atypical angucyclinones possessing an aromatic cleavage of the C-ring covers literature between 1995 and early 2020. The unusual framework of the middle C-ring, “broken” as a result of biotransformations and oxidations in vivo and bearing an sp3-C connection, is of interest for biosynthetic investigations. The reported 39 natural compounds (55 including stereoisomers) have been analyzed and arranged into three structural groups. The biosynthetic origin of all these compounds has been thoroughly reviewed and revised, based on the found connections with oxidized angucyclinone structures. The data on biological activities has been summarized. Careful consideration of the origin of the structure allowed us to outline a hypothesis on the biological function as well as prospective applications of such atypical angucyclinones.