Ru and Sm catalyzed polyaddition of dialdehydes to give polyesters. Application of Tishchenko type reactions to polymer synthesis

Tandem polymerization consisting of cyclotrimerization and the Tishchenko reaction: synthesis of acid- and alkali-degradable polymers with cyclic acetal and ester structures in the main chain

“…22–28 These reactions have been individually employed as bond-forming reactions for polymer synthesis because these reactions proceed with extremely high selectivity under appropriate conditions (Scheme 1 (i)). 29–33 Both reactions occur via the same intermediate that is generated by the coordination of a catalyst with an aldehyde. Therefore, we anticipated that an appropriate catalyst system could permit the simultaneous occurrence of these two reactions and allow for the incorporation of both cyclic acetal and ester structures into one polymer chain (Scheme 1 (ii)).…”

“…Finally, a hydrogen atom on the carbon atom, which was originally the carbonyl carbon, transfers to a newly coordinated aldehyde, resulting in the generation of an ester and an aluminum alkoxide. Although the Tishchenko reaction has been employed in polymer chemistry as a bond-forming reaction 30–33 and a termination reaction, 37 and for monomer synthesis, 38 there are no reports on the tandem polymerization consisting of the Tishchenko reaction and other organic reactions as far as we know.…”