Functional α,ω-dienes via thiol-Michael chemistry: synthesis, oxidative protection, acyclic diene metathesis (ADMET) polymerization and radical thiol–ene modification

Abstract

The synthesis of the novel α,ω-diene 2-(undec-10-en-1-yl)tridec-12-en-1-yl acrylate is described. Thiol-Michael coupling of this substrate followed by chemoselective oxidation of the thioether moiety with triazotriphosphorine tetrachloride (TAPC) furnished a suite of functional and symmetrical ADMET-active monomers in a quick and convenient manner. Polymerization of these adducts with Grubbs 1^st generation catalyst (RuCl₂(PCy₃)₂CHPh) was demonstrated to high conversion, and quantitative radical initiated thiol–ene modification of the backbone CC bonds was performed to impart additional functionality to each ADMET polymer. These reactions highlight the compatibility of thiol-based click chemistries for the preparation and post-modification of functional ADMET materials.