Abstract

AbstractThe total synthesis of gymnopusin (2) is described. The originally assigned structure for gymnopusin 1a was found to be incorrect by total synthesis using the Directed ortho‐Metalation (DoM)Cross‐CouplingDirected remote Metalation (DreM) sequence, a demonstrable key strategy for the regioselective construction of the 9‐phenanthrol core. The revised structure of gymnopusin (2) was confirmed by synthesis by adopting the same strategy but involving a key remote anionic Fries‐rearrangement step. Both routes highlight methodologies and concepts which may be of value in the regiocontrolled synthesis of phenanthrenoids specifically and in complex polycyclic aromatics in general.

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