Soluble and polymer-supported 2- and 3-benzylated furans were subjected to a sequence involving a Diels–Alderreaction with α,β-acetylenic carbonyl compounds, a Michael addition, and a subsequent retro-Diels–Alder reaction to yield olefinic compounds. On solid support, this traceless strategy is advantageous since pure compounds were released in the thermal cycloreversion step. The fur-2-ylated resin
an acetylenic dienophile to afford a thermally stable Diels–Alder adduct. Transformation of the adduct by Michael reaction with thiophenol has allowed an easy retro Diels–Alder reaction. This ‘safety-catch’ procedure leads to the formation of a chemically and stereochemicallypurealkene and to the regeneration of the polymer-bound furan.