α,ω-Reactive Building Blocks Based on a Dual Functional RAFT Agent for Thermal and Light-Induced Ligation

Marcel Langer; Jan O Mueller; Anja S Goldmann; Felix H Schacher; Christopher Barner-Kowollik

doi:10.1021/acsmacrolett.6b00267

α,ω-Reactive Building Blocks Based on a Dual Functional RAFT Agent for Thermal and Light-Induced Ligation

ACS Macro Lett. 2016 May 17;5(5):597-601. doi: 10.1021/acsmacrolett.6b00267. Epub 2016 Apr 27.

Authors

Marcel Langer^{1

2}, Jan O Mueller^{1

2}, Anja S Goldmann^{1

2}, Felix H Schacher^{3

4}, Christopher Barner-Kowollik^{1

2

5}

Affiliations

¹ Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76131 Karlsruhe, Germany.
² Institut für Biologische Grenzflächen, Soft Matter Synthesis Laboratory, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
³ Institute of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany.
⁴ Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7, 07743 Jena, Germany.
⁵ School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), Brisbane, QLD 4000, Australia.

PMID: 35632378
DOI: 10.1021/acsmacrolett.6b00267

Abstract

A dual functional chain transfer agent (CTA) capable of highly efficient sequential thermal and photoinduced ligation, generating α,ω-functional polymers, is introduced. The newly designed CTA (1-(4-((2-formyl-3-methyl phenoxy)methyl)phenyl)ethyl (diethoxyphosphoryl)methane dithioate) fuses thermally triggered hetero Diels-Alder chemistry with rapid light-induced photoenol chemistry. The versatility of the CTA is exemplarily demonstrated via the preparation of an amphiphilic triblock quaterpolymer poly(isoprene-co-styrene)-block-poly(ethyl acrylate)-block-poly(ethylene oxide) (P(I-co-S)-b-PEA-b-PEO). Subsequent to the homopolymerization of ethyl acrylate (PEA), a Cp-functional poly(isoprene-co-styrene) (P(I-co-S)) is conjugated with the electron-deficient C═S double bond (dienophile) of the CTA end group, generating a P(I-co-S)-b-PEA diblock terpolymer. The triblock quaterpolymer P(I-co-S)-b-PEA-b-PEO is generated by photoligation of a macromolecular dienophile, i.e., the fumarate-terminated poly(ethylene oxide) (PEO-fum) to the photoenol-functional P(I-co-S)-b-PEA. The new dual functional ligation RAFT agent constitutes a technology platform for generating α,ω-reactive building blocks from one single chain transfer agent.