Preparation of a Library of Poly(N-sulfonylimidates) by Cu-Catalyzed Multicomponent Polymerization.

Efficient synthesis of polyimidates has been a great challenge because of the difficulty of imidate bond formation and limited substrate scope. Here, we describe a successful method for the synthesis of various poly(N-sulfonylimidates) using Cu-catalyzed multicomponent polymerization (MCP). Minimizing water contamination in the polymerization, which results in low-molecular-weight oligomers, allows various combinations of three types of monomers (diynes, sulfonyl azides, and diols) that are bench stable and readily accessible, providing access to a library of polyimidates. Moreover, the formation of polyimidates is highly selective over the conventional click reactions. Most importantly, this report demonstrates a successful MCP that overcomes the drawbacks of previous MCP methods showing narrow monomer scope and producing low-molecular-weight polymers.