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The modular synthesis of biomass-based diols (BDOs) in a facile and general way remains a grand challenge. To surmount this hurdle, here we present a new synthetic route, namely employing a Passerini reaction followed by a thiol–ene click reaction, to prepare BDOs. By selecting readily available starting biobased materials, including acids, aldehydes, isonitriles, and hydroxythiol as the building blocks, this method offers a convenient and efficient way for accessing structurally diverse BDOs without the need for catalysts and under mild reaction conditions. Specifically, the ability of our method to precisely regulate BDOs’ aliphatic pendant chain length is demonstrated, which facilitates the development of waterborne polyurethane films with exceptional waterproof performance. By simplifying the BDO synthesis process, this method is poised to lead to a prosperous development for BDOs.

Graphical abstract: A facile, general, and modular synthetic approach to biomass-based diols

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