STEREOCHIMIE - LIII. CONTROLE ORBITALAIRE DE LA STEREOCHIMIE DES REACTIONS - IV HYDROCYANATION 1,4 DE CETO-3 Δ1-STEROIDES ET D'OCTALONES APPARENTEES

Article abstract of DOI:10.1016/S0040-4020(01)97658-6

Hydrocyanation at sites other than ring junctions does not exhibit the same stereoselectivity in the keto-3 Δ¹-steroid series as in analogous bicyclic compounds.Irrespective of the presence or the absence of an angular methyl group, the kinetic product has always an axial cyano group; however a stereoelectronic control of the reverse reaction explains why under thermodynamic conditions, only enones of the decalin series give both axial and equatorial epimers.A conformational analysis based on the conservation of the torsion angle and the maximum overlap of orbitals accounts for these facts.