ELECTROORGANIC REACTIONS .45. THE HIGHLY STEREOSELECTIVE ELECTROCHEMICAL HYDRODIMERISATION OF METHYL 4-TERT-BUTYLCYCLOHEX-1-ENECARBOXYLATE

UTLEY J., GÜLLÜ M., DEMATTEIS C., MOTEVALLI M., NIELSEN M.

TETRAHEDRON, vol.51, no.43, pp.11873-11882, 1995 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 51 Issue: 43
  • Publication Date: 1995
  • Doi Number: 10.1016/0040-4020(95)00748-w
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.11873-11882
  • Ankara University Affiliated: Yes

Abstract

Methyl 4-tert-butylcyclohex-1-enecarboxylate undergoes 1 F reduction at a mercury cathode in DMF solution to give as the major single product a hydrodimer in which the cyclohexyl rings are joined axially and the methoxycarbonyl groups are also axial. The structure is confirmed by X-ray crystallography. Kinetic experiments, combined with force field calculations, indicate radical-anion/radical-anion coupling which is under stereoelectronic control. and which dictates diaxial coupling of the cyclohexyl rings. Protonation of the resulting dimeric dianion is under thermodynamic control.