Total Synthesis of (−)-Enigmazole A

A highly convergent, stereocontrolled total synthesis of the architecturally complex marine sponge metabolite (−)-enigmazole A has been achieved. Highlights include an unprecedented late-stage large-fragment Petasis–Ferrier union/rearrangement, a multicomponent Type I Anion Relay Chemistry (ARC) tactic, and a dithiane–epoxide union in conjunction with an oxazole-directed stereoselective reduction.