The Stereochemistry of Rings A and B in 6-Substituted Δ4-3-Oxosteroids: A Study of H1 Allylic Spin-Spin Coupling in Systems with Defined Geometry

doi:10.1071/CH9631030

The Stereochemistry of Rings A and B in 6-Substituted Δ⁴-3-Oxosteroids: A Study of H¹ Allylic Spin-Spin Coupling in Systems with Defined Geometry

DJ Collins, JJ Hobbs and S Sternhell

Australian Journal of Chemistry 16(6) 1030 - 1041
Published: 1963

Abstract

The preparation of some 6-substituted A4-3-oxosteroids is described. As previously announced, the stereochemistry at the 6-position, which is of importance in connection with biological activity, may be deduced from examination of the N.M.R. signal due to the vinylic proton at C₄ which appears as a singlet (W_H = 1.5 - 1.8 c/s)in the 6β-substituted series and as a doublet (J = 1.6 - 1.8 c/s) in the 6α-substituted series. The general dependence of the allylic coupling constants on stereochemistry is examined and an empirical angular relation shown to exist, with the coupling constant at a maximum when the angle subtended between the allylic and vinylic protons is 90° and at a minimum when it is 0 or 180°. Theoretical implications are briefly considered.