Abstract
Hexasubstituted benzenoids are prepared by regioselective bimolecular [2 + 2 + 2] alkyne cyclotrimerizations of diynes with alkynes. These convergent and efficient benzannulations are directed toward and lead to the first total syntheses of the illudalane sequiterpenes fomajorin D and S, in 10 and 7 steps, respectively, from commercially available dimedone. Control experiments suggest that hydrogen bonding may play a role in preorganizing the diyne and alkyne coupling partners for establishing the desired regioselectivity, but other factors are likely involved in the selective formation of other regioisomers.