Thiol-Michael coupling and ring-opening metathesis polymerization: facile access to functional exo-7-oxanorbornene dendron macromonomers

This paper describes the synthesis of the 2- and 4-functional acrylic exo-7-oxanorbornene species 2-((2-((3aR,7aS)-1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-epoxyisoindol-2-yl) ethoxy) carbonyl)-2-methylpropane-1,3-diyl diacrylate and (((2-((2-((3aR, 7aS)-1,3-dioxo-1,3,3a, 4,7,7a-hexahydro-2H-4,7-epoxyisoindol-2-yl) ethoxy) carbonyl)-2-methylpropane-1,3-diyl)bis(oxy))bis(carbonyl))bis(2-methylpropane-2,1,3-triyl) tetraacrylate, and their use as common precursors for the preparation of a small library of dendronized thioether adducts via nucleophile-mediated thiol-Michael coupling chemistry. We subsequently demonstrate that the dendronized monomers can be (co) polymerized via ring-opening metathesis polymerization employing Grubbs'-type Ru-based initiators to give novel functional dendronized (co) polymers of predictable molecular weights and acceptable dispersities (D-M = (M) over bar (w)/(M) over bar (n)). (C) 2013 Society of Chemical Industry