Orthogonal Thiol Addition Chemistry Based on Ether Acrylates

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.