Abstract A method is described for the synthesis of isotopomers of cortexolone from the commercially available andros-4-ene-3, 17-dione. The strategy is based on the use of K ¹³ CN for labeling at position 20 and of ¹³ CH 3 MgI, generated in situ, for labeling at position 21. Because of the early introduction of the [¹³ C] labeling, our efforts aimed at reproducible experimental procedures giving high yields with respect to the isotope containing ...