Transition‐Metal‐Catalyzed Carbene Transformations for Polymer Syntheses

Polymerization using diazocarbonyl compounds as a monomer is described. Diazoacetates can be polymerized to afford C–C main chain polymers bearing an alkoxycarbonyl group on each main chain carbon atom. Some Pd-complexes with a η 3 -anionic ligand are effective as an initiator for the polymerization. The ester substituents are densely-packed around the C–C main chain, resulting in the formation of polymers with unique properties. Bis(diazocarbonyl) compounds can be used as a monomer for polycondensation in three mode: three, two, and single component polycondensation. Distinctive reactivities of diazocarbonyl groups realized syntheses of polymers with a variety of new repeating unit structures.