13C NMR spectral assignment of five epimeric 3α-versus 3β-functionalized cholestane pairs

13C NMR chemical shift assignments of five α- and β- epimeric pairs of cholestanes functionalized at C-3 are presented. Empirical increment estimations proved to be a valuable tool for the unequivocal structural elucidation when compared with the chemical shift values of cholestanes derivatized by introduction of N- and S-containing groups at C-3 in equatorial and axial positions. Moreover, the possibility is demonstrated to anticipate the effect of OC(S)R substituents at neighboring carbon atoms of the ring A backbone. Copyright © 2005 John Wiley & Sons, Ltd.