Poly(β-trimethylsilyloxy ester): A Degradable Polymer Based on Retro Mukaiyama Aldol Reaction

Herein, a new type of degradable poly(beta-trimethylsilyloxy ester) prepared by the organocatalyzed Mukaiyama aldol polyaddition between bis(silyl ketene acetal)s and dialdehydes is reported. Specifically, the t-Bu-P-4-catalyzed polyaddition between 1,2-bis[2-methyl-1-(trimethylsiloxy)prop-1-enyloxy]ethane (MTS2) and 4,4'-biphenyldicarboxaldehyde (BPDA) or butane-1,4-diyl bis(4-formylbenzoate) (BDA) can produce poly(beta-trimethylsilyloxy ester)s with number-average molar mass greater than 10 kg mol(-1). For the first time, it is found that these poly(beta-trimethylsilyloxy ester)s are degradable in solution in the presence of nucleophiles such as fluoride and cyanide anions. It is also found that the degradation behavior of poly(beta-trimethylsilyloxy ester)s is highly dependent on the nature of the used catalyst and the bond scission in polymer is fundamentally rooted in the retro Mukaiyama aldol reaction mechanism.

Automated summary

A new type of degradable poly(beta-trimethylsilyloxy ester) was synthesized by the organocatalyzed Mukaiyama aldol polyaddition. These polyesters showed degradation behavior in the presence of nucleophiles, and the degradation mechanism was influenced by the nature of the catalyst used.