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, cilt.51, sa.43, ss.11873-11882, 1995 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 51 Sayı: 43
  • Basım Tarihi: 1995
  • Doi Numarası: 10.1016/0040-4020(95)00748-w
  • Dergi Adı: TETRAHEDRON
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.11873-11882
  • Ankara Üniversitesi Adresli: Evet

Özet

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.