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.