Divergent Synthesis of Pyrone Diterpenes via Radical Cross Coupling

A divergent strategy for assembling
pyrone diterpenes is presented.
Capitalizing on the unique stereo- and chemoselectivity features of
radical-based chemistry, the core decalin of these structures is efficiently
forged using an electrochemically assisted oxidative radical polycyclization
while key peripheral substituents are appended using decarboxylative
radical cross couplings. In this way, access to four natural products
(subglutinols A/B, higginsianin A, and sesquicillin A) is achieved
in a concise and stereocontrolled fashion that is modular and amenable
to future medicinal chemistry explorations.