An Enantioselective Biomimetic Total Synthesis of (−)‐Siccanin

A convergent asymmetric synthesis of the clinically important antifungal agent (−)-siccanin (1) mimics the proposed biosynthetic pathway. A Pd-catalyzed asymmetric allylic alkylation was used to establish the stereochemistry, and sequential radical processes (a TiIII-promoted cyclization followed by diacetoxyiodobenzene-promoted tetrahydrofuran formation) led to the completion of the first asymmetric synthesis of 1.