Visible‐Light‐Induced Passerini Multicomponent Polymerization

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 carboxy...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-04, Vol.58 (17), p.5672-5676
Main Authors: Tuten, Bryan T., De Keer, Lies, Wiedbrauk, Sandra, Van Steenberge, Paul H. M., D'hooge, Dagmar R., Barner‐Kowollik, Christopher
Format: Article
Language:English
Subjects:
Aldehydes
Carboxylic acids
Chemical synthesis
Ketones
multicomponent reactions
Passerini reaction
photochemistry
Polymerization
Polymers
reaction kinetics
Side reactions
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Summary: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. Lights on: Passerini multicomponent polymerizations can be triggered with mild visible light utilizing photocaged thioaldehydes. The complex, high reactivity of thioaldehydes is optimized through stochastic kinetic Monte Carlo simulations to yield highly functional soft‐matter materials capable of being degraded as well as chain expanded.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201901506