Abstract The stereostructures of some condensed-skeleton cis-and trans-dihydro-1, 3- thiazines and 1-thia-2-phenyl-3-azaspiro [4n+ 1] alk-2-enes (n= 3–6) were established by 1 H and 13 C NMR spectroscopy. A comparative study indicated that the cis-thiazines have greater conformational mobility than the corresponding oxazines, although the preferred conformer of the two types of cis compounds is the same, with the sulphur axial and the 4- ...