Facile Synthesis of Sequence-Regulated Synthetic Polymers Using Orthogonal SuFEx and CuAAC Click Reactions.

The orthogonal sulfur-fluoride exchange reaction (SuFEx) and copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) are employed to synthesize sequence-regulated synthetic polymers. The high efficiency and broad tolerance of SuFEx and CuAAC to diverse chemical functionalities enable the one-pot synthesis of polydispersed sequence-controlled polymers by step-growth copolymerization in high yield and sequence complexity. Furthermore, iterative SuFEx and CuAAC coupling reactions on a solid support, without the need of protecting groups, afford monodispersed sequence-defined oligomers. The use of this orthogonal pair of click reactions provides new opportunities to facilely access sequence-regulated synthetic polymers with a high degree of structural diversity.