Abstract Ring A proton shifts and couplings and 13 C shifts of all carbons are given for 17β- acetoxy-2α-methyl-and 17β-methoxy-2β-methyl-5α-androstan-3-one and 2, 2-dimethyl-17β- methoxy-5α-androstan-3-one. It was concluded that the 2β-methyl derivative exists with ring A in a regular chair conformation while the 2β-methyl derivative exists with ring A in an inverted boat conformation with C-2 and C-5 at the bow/stern positions. The data for 2, 2- ...