Efficient synthesis and subsequent transformations of phenylsulfanylbicyclo[2.2.2]octenones and phenylselenylbicyclo[2.2.2]octenones.

Inverse-electron-demand Diels-Alder reactions of masked o-benzoquinones 2 with phenyl vinyl sulfide and phenyl vinyl selenide furnished highly functionalized bicyclo[2.2.2]octenone derivatives 3 and 4, respectively, in excellent regio- and stereoselectivities and yields up to 90%.