De Mayo reaction of dimedone with allene results in the formation of 3, 3-dimethyl-7- methylenecycloocta-1, 5-dione 6 together with the corresponding head-to-tail adduct 5 which spontaneously dimerizes to the hetero Diels-Alder adduct 7. Reduction of 6 together with sodium borohydride or Grignard reagents affords the transannular hemiketals 9 which can easily be isomerized (DBU) to their conjugated analogues 10. Depending on the ...