Visible‐Light‐Induced Passerini Multicomponent Polymerization

Abstract

Herein, we introduce an additive-free visible-lightinduced Passerini multicomponent polymerization (MCP) for the generation of high molar mass chains.Inplace of classical aldehydes (or ketones), highly reactive,insitu photogenerated thioaldehydes are exploited along with isocyanides and carboxylic acids.P rone to side reactions,t he thioaldehyde moieties create ac omplex reaction environment which can be tamed by optimizing the synthetic conditions utilizing stochastic reaction path analysis,h ighlighting the potential of semibatch procedures.O nce the complex MCP environment is understood, step-growth polymers can be synthesized under mild reaction conditions which-after aM umm rearrangement-result in the incorporation of thioester moieties directly into the polymer backbone,leading to soft matter materials that can be degraded by straightforwarda minolysis or chain expanded by thiirane insertion.

Catalyst‐Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4‐Dibromo‐2,3‐Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups

“…[ 1 ] Multicomponent polymerization (MCP) has become a powerful tool for obtaining multifunctional advanced materials due to its excellent structural diversity, mild reaction conditions, and environmental benefits, and has thus attracted much attention. [ 2–11 ] In recent years, triple‐bond compounds, such as isonitriles [ 12–17 ] and alkynes, [ 18–24 ] have been widely used to prepare novel polymers through MCP. For instance, in 2018, Li et al.…”

Facile Multicomponent Polymerization and Postpolymerization Modification via an Effective Meldrum's Acid‐Based Three‐Component Reaction

“…[ 11,12 ] Recently, multicomponent reactions have received more and more attention in the community of polymer chemistry. [ 13,14 ] Isocyanide‐based multicomponent reactions, [ 15–21 ] alkyne‐based multicomponent reactions, [ 22–26 ] and others [ 27–32 ] have been used in polymer conjugation, and combination with living/controlled polymerization to produce functional polymers with various macromolecular architectures. [ 33–36 ] Most importantly, the direct multicomponent polymerizations and multicomponent tandem polymerizations contributed many unconventional polymers with sufficient complexity and interesting properties [ 13,16,18,26,37 ] .…”

Multicomponent Reactions in Polymer Chemistry Utilizing Heavier Main Group Elements

“…We demonstrated that through careful stochastic modelling that catalyst free, visible light induced thioaldehydes can be generated and polymerized in‐situ via a Passerini mechanism ( Scheme ). [ 40 ] In addition to the mild wavelength of light needed for such a polymerization, there were added benefits in harnessing thiocarbonyl compounds in such a polymerization. By using photo generated thioaldehydes, the final polymer backbone—after the Mumm rearrangement—has a thioester directly incorporated into the repeat unit, bypassing the need to synthesize a thioester containing monomer.…”