Biomimetic syntheses of the litseaverticillols A-G, I and J are reported herein. The syntheses rely heavily on the application of two different modes of reaction for photochemically generated singlet oxygen, namely, the [4+2] cycloaddition of singlet oxygen (1O2) with furans and the ene reaction of 1O2 with double bonds. The highlight of these syntheses is a one-pot cascade sequence, involving five synthetic operations initiated by a [4+2] reaction, to form the fully functionalised litseaverticillol core. A series of regioselective ene reactions are then used to appositely functionalise the side chains. The synthesis of litseaverticillol E (both its originally proposed and its actual structures) allows a structural reassignment of this natural product.