This work reports the total syntheses of Isodon diterpenes trichorabdal A and maoecrystal Z via a common bicyclo[3.2.1]octane intermediate, which chemically bridges the two distinct structures through a retro-aldol/aldol reaction cascade. Other synthetic features include an efficient cross-ring radical cyclization for rapid construction of an all carbon quaternary center commonly seen in Isodon diterpenoids, a challenging Ueno-Stork cyclization on to a sensitive 1,6-enone system, as well as a serial of chemoselective functional group manipulations in complex chemical environments.
A concise total synthesis of mersicarpine is achieved by exploiting a cyclic carbamate for generation of a tertiary carbocation. The key step involves intramolecular Friedel-Crafts alkylation with this carbocation for the construction of a quaternary carbon center and a subsequent oxidation and cyclization cascade for the formation of a seven-membered cyclic imine. The chemistry allowed for a rapid one-pot synthesis of mersicarpine from a simple intermediate using straightforward chemical operations.
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