Controlled switching thiocarbonylthio end-groups enables interconvertible radical and cationic single-unit monomer insertions and RAFT polymerizations.

To emulate the ordered arrangement of monomer units found in natural macromolecules, single-unit monomer insertion (SUMI) have emerged as a potent technique for synthesizing sequence-controlled vinyl polymers. Specifically, numerous applications necessitate vinyl polymers encompassing both radically and cationically polymerizable monomers, posing a formidable challenge due to the distinct thiocarbonylthio end-groups required for efficient control over radical and cationic SUMIs. Herein, we present a breakthrough in the form of interconvertible radical and cationic SUMIs achieved through the manipulation of thiocarbonylthio end-groups. The transition from a trithiocarbonate (for radical SUMI) to a dithiocarbamate (for cationic SUMI) is successfully accomplished via a radical-promoted reaction with bis(thiocarbonyl) disulfide. Conversely, the reverse transformation utilizes the reaction between dithiocarbamate and bistrithiocarbonate disulfide under a cationic mechanism. Employing this strategy, we demonstrate a series of synthetic examples featuring discrete oligomers containing acrylate, maleimide, vinyl ether, and styrene, compositions unattainable through the SUMI of a single mechanism alone.