A synthesis of the structurally fascinating fungal metabolite UCS1025A (1) was accomplished. It features a likely biomimetic approach to the octalin subunit via an intramolecular Diels-Alder (IMDA) reaction of a putative triene precursor (2), preceded by an efficient construction of the bisheteratriquinane subunit within that compound. Specifically, an intramolecular silyl triflate-induced cyclization of an in situ-generated silyl ketene acetal onto an imide carbonyl group (e.g., 7 to 8) was developed. The IMDA relative reactivities of a family of valence bond isomers, each differing in the precise nature of the dienophilic subunit, were determined. Under biologically relevant conditions (D2O, pH 7.2 buffer, ca. 25 °C), triene 2, via its lactone ring-opened congener, underwent very fast (t1/2 = 10 min) conversion to the ring-opened forms of 1 (i.e., 5a) and the tetraepimeric, alternative endo-adduct, 3 [i.e., (tetraepi)-5a].