13C nuclear magnetic resonance study of 17 alpha-substituted estradiols.

We report the 13C NMR data for 20 compounds bearing a substituent (alkyl, alkenyl, alkynyl, alkylamide, spiro-gamma-lactone, phenyl, benzyl, naphthyl, etc.) at the 17 alpha-position of estradiol. The carbon assignments were done using 1D and 2D NMR experiments (distortionless enhancement by polarization transfer, homonuclear correlated spectroscopy, heteronuclear shift correlation, and heteronuclear shift correlation via long-range couplings). Only the chemical shifts of carbons 12-18, which surround the substitution site, were affected by the addition of a substituent. The magnitude of the effects (shielding or deshielding) was influenced by the 17 alpha-substituent. The individual effects at these carbons were sufficiently distinctive to identify specific centers and should be valuable for signal assignment of a variety of 17 alpha-derivatives of estradiol. In addition to carbon-skeleton assignment, we also report the carbon-substituent assignments.