The manuscript is an overview on methods for the in situ generation and applications of highly reactive thiocarbonyl S-sulfides. Typically, they react as sulfur rich 1,3-dipoles and trap both electron deficient C,C dipolarophiles and thiocarbonyl substrates yielding the corresponding five membered cycloadducts. In some instances, intermediate thiocarbonyl S-sulfides and/or their cyclic isomers, i.e. dithiiranes, act as sulfur transferring agents leading to sulfur rich heterocyles (pentathiepanes, hexathiepanes, etc.).