Thiepanes and Thiepines

In this chapter, the monocyclic, benzo and dibenzo-fused ring systems, thiepine, thiepane, 1-benzothiepine, 2-benzothiepine, 3-benzothiepine, dibenzo[b,d]thiepine, dibenzo[b,e]thiepine, dibenzo[b,f]thiepine, dibenzo[c,e]thiepine and their carbocycle and heterocycle-fused systems are included. Further dihydro, and tetrahydro derivatives and their bridged bicyclic analogs are also described, as well as the corresponding sulfoxides and sulfones. The present chapter is intended to update the previous work on thiepines and thiepanes, and covers literature published since 2008. Theoretical studies on thiepine-benzene sulfide valence isomerization have been of continuous interest. In addition, the theoretical interest related to aromaticity and anti-aromaticity has been studied. Furthermore, fused systems, such as dibenzo[b,f]thiepines has become important structural motifs found in a diverse array of biologically active molecules. In the last decade, many reports on the synthesis and reactions of thiepines by transition-metal catalysts have appeared.