An Annulation Reaction for the Synthesis of Cross-Conjugated Triene-Containing Hydroindanes from Acyclic Precursors

In efforts directed toward the synthesis of seco-prezizaane sesquiterpenoids, a stereoselective annulation reaction has been developed between 4-hydroxy-1,6-enynes and TMS-alkynes that delivers cross-conjugated triene-containing hydroindanes. Contrary to previous reports, enyne substrates bearing two propargylic ethers enable the presumed organometallic intermediate to be trapped by double elimination. The tendency of products from this annulation to undergo Diels-Alder-based dimerization was harnessed to accomplish a two-step complexity-generating sequence en route to densely functionalized carbo- and heteorocyclic systems.