Bisketene Equivalents as Diels–Alder Dienes

2,5-Bis­(tert-butyldimethyl­silyloxy)­furans are established as vicinal bisketene equivalents for application as dienes in the Diels–Alder reaction. Cycloaddition with olefinic dienophiles, under exceptionally mild conditions, enables convergent access to highly substituted para-hydroquinones in unprotected form via a one-pot Diels–Alder/ring-opening/tautomerization sequence. The synthesis of para-benzoquinones from acetylenic dienophiles, including benzynes, is also demonstrated, and 2,5-bis­(tert-butyl­dimethyl­silyloxy)­pyrroles are established as competent dienes for the synthesis of para-iminoquinones. Application in natural product synthesis enables gram-scale access to the neuroprotective agent (±)-indanostatin.