Total Synthesis of (−)‐Spiroleucettadine

Abstract

AbstractOne of a number of intriguing new alkaloids isolated from the Leucetta sp. sponge in 2004, spiroleucettadine displayed unique structural features on a restricted scaffold: a trans‐fused 5,5‐bicyclic ring system together with an amino hemiketal moiety. Attempts to synthesize the initially proposed structure failed, raising questions as to its veracity, and structure revision ensued in 2008; no successful synthetic approach has been reported to date. Herein, we describe the enantiospecific total synthesis of (−)‐spiroleucettadine by a highly efficient biomimetic approach starting from l‐tyrosine. One of two key hypervalent‐iodine‐mediated oxidation reactions forged the spirocyclic cent..