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A biomimetic synthesis of briareolate ester B (3) from briareolate ester L (1) via the intermediate briareolate ester G (2) has been achieved through a unique transannular oxa-6π electrocyclization induced by UVA light. UVC irradiation of 3 triggered a rapid retro-6π electrocyclization to establish an unprecedented photochromic switch. In the ground state, reaction of 1 led to the formation of a polycyclic γ-spiroketal γ-lactone 5, architecturally related to the ether-bridged cembranoids of the cladiellin class.