Synthesis and stereochemistry of 1H,5H-naphtho[1,8-ef][1,3]dithiocine 2-oxides

3-Substituted 1H,5H-naphtho[1,8-ef][1,3]dithiocines (R. = H, Me, Ph, t-Bu) were oxidized with m-chloroperoxybenzoic acid to the corresponding 2-oxides having trans configuration (R : H). According to C the H-1 and C-13 NMR data (including NOESY experiments), the disubstituted compounds at room temperature exist in a boat conformation with equatorial orientation of the substituent on C-3 and oxygen atom on S-2. The compound with no substituent on C3 gives rise to a mixture of boat conformers with axial and equatorial sulfoxide oxygen atoms at a ratio of 83:17.