A Formal 1,2-Stevens\nRearrangement of Thioester Ylides\nas a Single-Atom Molecular Editing Tool

A rhodium-catalyzed\nreaction of thioesters with diazo reagents\nwas recognized as a powerful and unprecedented tool for single-atom\nmolecular editing by the insertion of a single carbon atom into the\nC(O)S thioester bond, thereby leading to various α-thioketones\npossessing a quaternary carbon atom. A selective and precise defunctionalization\nof the polyfunctionalized products further demonstrated the synthetic\nutility of the reaction for the synthesis of more common structural\nclasses of compounds.