Premium
Visible‐Light‐Induced Passerini Multicomponent Polymerization
Author(s) -
Tuten Bryan T.,
De Keer Lies,
Wiedbrauk Sandra,
Van Steenberge Paul H. M.,
D'hooge Dagmar R.,
BarnerKowollik Christopher
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901506
Subject(s) - aminolysis , thiirane , thioester , polymerization , polymer , molar mass , chemistry , polymer chemistry , in situ , polystyrene , photochemistry , materials science , combinatorial chemistry , organic chemistry , catalysis , ring (chemistry) , enzyme
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.