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On the action of a Lewis acid, 2,2-dimethoxyethyl acrylate is readily transformed into a reactive cationic dienophile, and it reacts with dienes under mild conditions to give Diels-Alder adducts in good yields with high stereo-and/or regioselectivity. 2-Oxopropyl acrylate and 2-oxocyclopentyl acrylate are also found to be converted into alternative cationic dienophiles by a facile procedure.

Starting from optically active 5-trimethylsilyl-2-cyclohexen-1-one derivatives, the title dienes were synthesized by using silicon-mediated 1,4-elimination as a key step. A straightforward synthesis of the unnatural enantiomer of (−)-dictyopterene C′ utilizing the method was also carried out.

A phytotoxin, solanapyrone E, has been synthesized from the decalone prepared by the domino Michael reaction of the kinetic enolate of optically pure acetylcyclohexene with methyl crotonate. After several transformations on the decalone ring, condensation of a methyl acetoacetate equivalent installed a pyrone moiety and introduction of a hydroxymethyl unit into the pyrone ring furnished solanapyrone E.