Herein, we introduce an additive-free visible-light-induced Passerini multicomponent polymerization (MCP) for the generation of high molar mass chains. In place of classical aldehydes (or ketones), highly reactive, in situ photogenerated thioaldehydes are exploited along with isocyanides and carboxylic acids. Prone to side reactions, the thioaldehyde moieties create a complex reaction environment which can be tamed by optimizing the synthetic conditions utilizing stochastic reaction path analysis, highlighting the potential of semi-batch procedures. Once the complex MCP environment is understood, step-growth polymers can be synthesized under mild reaction conditions which-after a Mumm rearrangement-result in the incorporation of thioester moieties directly into the polymer backbone, leading to soft matter materials that can be degraded by straightforward aminolysis or chain expanded by thiirane insertion.
Keywords: Passerini reaction; multicomponent reactions; photochemistry; polymerization; reaction kinetics.
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