We herein report an efficient and systematic synthesis of 1-pyrrolines from cyclobutyl azides under thermal and neutral conditions. The reaction proceeded without any additional reagents, and nitrogen was generated as the sole by-product. Furthermore, the generated 1-pyrrolines could be continuously transformed into pyrroles, N-Boc-amines, and oxaziridines in an one-pot manner.
For the first time, an approach to 3,4-disubstituted thietes was developed through two complementary paths. While the first one relies on α-metalation, the second is based on direct C–H functionalization. A new library of sophisticated sulfur-containing four-membered rings is described, paving the way to new bioactive analogues and small heterocycle incorporation.