The catalytic Staudinger–Vilarrasa (S–V) reaction, a widely utilized reaction for synthesizing amide-containing compounds, has played vital roles in organic synthesis. In this work, we introduce this reaction as a highly efficient chemistry strategy for the first time in polymer chemistry. First, the polycondensation of dicarboxylic acids with organic diazides produces a series of polyamides in yields of up to 94% and high molecular weight of 28 kDa. Second, this reaction between polymer-N3 and various functional organic acids yields amide-end-functionalized polymers with near 100% efficiency. Third, amide-linked (multi)block copolymers (PEG-PEG, PS-PS, PS-b-PEG, PtBA-b-PEG) with approximate 100% efficiency, a star polymer (PEG)3 with ∼95% efficiency and side-chain amide-functionalized polymers (∼100% efficiency) are constructed via this reaction between polymers and organic acids or polymers. This highly efficient catalytic S–V reaction provides a programable platform for producing amide bond-containing polymers that compares favourably with previous reported click strategies, such as CuAAC, thiol–ene and Diels–Alder reactions in some ways.
