A CONCISE SYNTHESIS OF THE 2,3-DIMETHYLENE-1,4-METHANO-1,2,3,4-TETRAHYDRONAPHTHALENE AND ITS REACTION WITH SINGLET OXYGEN


ATASOY B., BAYRAMOGLU F., HOKELEK T.

TETRAHEDRON, vol.50, no.19, pp.5753-5764, 1994 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 50 Issue: 19
  • Publication Date: 1994
  • Doi Number: 10.1016/s0040-4020(01)85643-x
  • Title of Journal : TETRAHEDRON
  • Page Numbers: pp.5753-5764

Abstract

Palladium-catalyzed carbomethoxylation of benzonorbornadiene (7) yielded dimethyl-1,4-methano-1,2,3,4-tetrahydronaphthalene-2,3-dicarboxylate (9) which was transformed in three steps into 2,3-dimethylene-1,4-methano-1,2,3,4-tetrahydronaphthalene (4) in a high yield. Reaction of 4 with singlet oxygen resulted in the formation of epoxy-endoperoxide (12). X-ray crystallographic analysis demonstrated that epoxide ring is exo as methylene bridge. For the first time, the epoxy-endoperoxide formation from the ''one pot'' reaction of a diene with singlet oxygen was observed. The epoxy-endoperoxide formation mechanism was discussed. CoTPP (Cobalt(II)tetraphenylporphyrin) catalyzed rearrangement of epoxy-endoperoxide gave hydroxy-aldehyde (13) which was oxidized into dialdehyde (14).