Designer Template Initiator for Sequence Regulated Polymerization: Systems Design for Substrate-Selective Metal-Catalyzed Radical Addition and Living Radical Polymerization

"Template initiator" platforms (1) have been designed for expressing the sequence information in a template in radical polymerization. Thus, we demonstrated the structural adequacy of 1 consisting of two initiating sites placed ortho to each other in benzene: one for living cationic polymerization to introduce a template carrying substrate-recognition tags, and the other for metal-catalyzed living radical polymerization to achieve sequence regulation. For example, for two positional isomers with an amine template for an acid monomer, only the ortho initiator induced selective radical addition of MAA (recognizable) over MMA (non-recognizable). Another version was an oligo(vinyl ether) with a multiple amine template, which demonstrated template effects for MAA recognition over BzMA in copolymerization.