Having developed a stereoselective entry point to the 5-8-5 motif, we preceded to apply this chemistry to a model of the ophiobolin nucleus. We noted previously that the attachment of electron-withdrawing groups to the furan in 9 shuts down the requisite photocycloaddition. Thus, as outlined in Scheme 5, we opted to start from furan 17. This species was elaborated to alcohol 18 in 74% yield via a Heck reaction with 2-hydroxy-3-butene and addition of ethynylmagnesium bromide to the resultant ketone. Fragment 18 was then coupled with enone 16 as shown in Scheme 2 to furnish 9h in 70% yield. Photoinduced cycloisomerization of 9h using a modification of our standard protocol, 30 followed by protection of the C3 alcohol, gave 19 in 62% yield (13:1 d.r. at C3). The requisite angular methyl group was introduced using Me2CuLi and TMSCl to provide 20 as a single diastereomer. This intermediate was isolated in >95% yield and was found to be stable for several weeks at -20 ºC. Alternatively, unpurified solutions of 20 in THF could be treated with BBr3 at 0 °C to afford alcohol 21 in 88% yield from 19. Following an extensive screen of dehydrating reagents, the regioselective dehydration of 21 was realized using Martin's sulfurane (22). In this case, it was necessary to treat the reaction mixture with aq. TBAF to unveil the C3 alcohol before workup. This highly optimized procedure gave triene 23 in 72% yield. Finally, an epoxidation of the A-ring alkene was accomplished with catalytic VO(acac)2 and TBHP as an oxidant. As predicted, this reaction was effectively directed by the C3 tertiary alcohol to generate epoxide 24 (>20:1 d.r.) in 90% yield. The relative stereochemistry of 24 was established by single crystal X-ray diffraction.