Abstract: | The γ-effects of sulphur on 13C NMR chemical shifts have been measured in a series of steroidal compounds containing the thiophene ring in different configurations with respect to the rest of the molecule. The data constitute the first example of downfield effects exerted by sulphur on both gauche and antiperiplanar γ-carbons. The γ-gauche effect of sulphur amounts to 1.6–1.8 ppm, the γ-antiperiplanar effect from practically zero to almost 1 ppm. |