Synthesis of functional polymers by the Pd-mediated polymerization of diazoacetates and polycondensation of bis(diazocarbonyl) compounds

Our recent studies on the polymerization of diazocarbonyl compounds to afford functional polymers are reviewed. In the first part of this article, the Pd-mediated polymerization of diazoacetates is described. Various functionalized diazoacetates with ester substituents were prepared and polymerized with Pd-based initiating systems to yield poly(substituted methylene)s (PSMs) with functional groups on each carbon atom in the main chain. The physical and chemical properties of the resulting functionalized PSMs were examined relative to those of their vinyl polymer counterparts [poly(substituted ethylene)s] possessing the same functional groups on every other carbon atom, and enhanced properties due to the effects of the dense packing of the functional groups in the PSMs were observed in some examples. The second part of this report summarizes our recent results on the polycondensation of bifunctional diazocarbonyl compounds as monomers. Three successful examples, namely, (1) the synthesis of well-defined unsaturated polyesters by the transition metal-catalyzed, single-component polycondensation of bis(diazoacetate)s, (2) the preparation of a new type of aromatic polyamine by the polycondensation of bis(diazoacetate)s with aromatic diamines, and (3) the multicomponent polycondensation of bis(diazocarbonyl) compounds affording an unprecedented acid-degradable polymer, poly(β-keto enol ether), are described. Our recent studies on the polymerization of diazocarbonyl compounds to afford functional polymers are reviewed. In the first part of this article, Pd-mediated polymerization of various functionalized diazoacetates and unique properties of the resulting polymers due to the effects of the dense packing of the functional groups in the polymers are described. The second part of this report summarizes our recent results on the polycondensation of bifunctional diazocarbonyl compounds as monomers.