Unusual endoperoxide isomerizations: a convenient entry into 2-vinyl-2-cyclopentenones from saturated fulvene endoperoxides.

An unusual peroxide base promoted isomerization was uncovered. Saturated endoperoxides derived from fulvenes give rise to 2-vinyl-2-cyclopentenones upon treatment with DBU in CH(2)Cl(2) in a one-pot reaction. This methodology was applied to a convenient synthesis of dihydrojasmone. Moreover, functional groups placed on the side chain at C-6 participate in the base catalyzed isomerizations via conjugate attack at the enone moiety to give 2-cyclopentenones carrying oxygen heterocycles at C2.