Thai Linh Duy, Neumaier Marco, Barner-Kowollik Christopher
Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD 4000, Australia.
J Am Chem Soc. 2025 Jul 2;147(26):22363-22367. doi: 10.1021/jacs.5c08202. Epub 2025 Jun 18.
The thiol-Michael and radical thiol-ene addition chemistries are extremely powerful tools for the construction of advanced soft matter materials. However, a critical challenge of these chemistries lies in their nonideal orthogonality in which both acrylates (Michael acceptors) and electron-rich olefins are active in a radical thiol-ene reaction. Herein, we show that by employing an ether acrylate (β-alkoxyacrylate), readily accessible via the efficient hydroxyl-yne click reaction, true orthogonality between activated double bonds can be achieved. Critically, we exploit the radical inactive property of the ether acrylate for the efficient synthesis of difficult-to-prepare sequence-defined main-chain macromolecular photoswitches and brush-like polymers. The results reported open a straightforward opportunity to synthetically access advanced materials with controllable properties.
硫醇-迈克尔加成反应和自由基硫醇-烯加成反应化学是构建先进软物质材料的极为强大的工具。然而，这些反应化学面临的一个关键挑战在于它们的正交性不理想，即丙烯酸酯（迈克尔受体）和富电子烯烃在自由基硫醇-烯反应中均具有活性。在此，我们表明，通过使用可经由高效的羟基-炔点击反应轻松获得的醚丙烯酸酯（β-烷氧基丙烯酸酯），可以实现活化双键之间真正的正交性。至关重要的是，我们利用醚丙烯酸酯的自由基惰性特性高效合成难以制备的序列定义主链大分子光开关和刷状聚合物。所报道的结果为合成具有可控性质的先进材料提供了直接的机会。
