Total Synthesis of Angucyclines, 1. – Synthesis of a Daunomycinone–Rabelomycin Hybrid

The synthesis of the racemic angucyclinone hybrid 3 which combines the structural features of rabelomycin (1) and daunomycinone (2) is described. Key steps are the cyclization of the bromide 6b by a Marshalk‐type reaction to yield the angular skeleton 7b, introduction of the tertiary hydroxy group by bromination to 11, solvolysis to 12 and photoinduced oxygenation to afford the C‐1 ketone 3.