Single-unit monomer insertion (SUMI) has become an important
strategy
for the synthesis of sequence-controlled vinyl polymers due to its
strong versatility and high efficiency. However, all reported SUMI
processes are based on a free-radical mechanism, resulting in a limited
number of monomer types being applicable to SUMI or a limited number
of sequences of structural units that SUMI can synthesize. Herein,
we developed a novel SUMI based on a cationic mechanism (cSUMI), which
operates through a degenerative (similar to radical SUMI) but cationic
chain transfer process. By optimizing the chain transfer agent (CTA)
and monomer pairs, a high-efficiency cSUMI was achieved for vinyl
ether and styrene monomers. Based on this reaction, a range of discrete
oligomers containing vinyl ether and styrene moieties, and even α-/ω-end
and in-chain sequence-regulated polymers were synthesized, most of
which cannot be achieved by radical SUMI. In addition, we explored
the application of these sequence-regulated polymers in the preparation
of miktoarm star polymers, delivery of photosensitizers, and solubilization
of fluorescence probes. The development of SUMI with a new mechanism
will certainly broaden the scope of structures and sequences in precise
vinyl-based polymers.