Synthesis of Enantiomeric ω-Substituted Hydroxy Acids from Terminal Epoxides and Alkenes: Functional Building Blocks for Discrete and Sequence-Defined Polyesters

Polyesters exhibiting a protein-like absolute atomic precision have unlimited potential for application as biomaterials and polymeric materials. Herein, we report the synthesis of enantiomeric omega-hydroxy acids (OHAs) from terminal epoxides and alkenes as starting materials. Our synthetic strategy allows the synthesis of a library of OHAs with a well-defined atomic composition (carbon number), stereochemical configuration, and substituent chemistry. These monomers can serve as building blocks for the preparation of discrete and sequence-defined polyesters, wherein various functional groups can be introduced at specific locations via the cross-convergent method. We demonstrated that the specific locations of the reactive functional groups of the sequence-defined polyester could be utilized to form a concentrically cyclic polymer upon cyclization. Our results provide a facile platform for engineering polyesters with the structural sophistication exhibited only by biopolymers, such as proteins and nucleic acids.

Automated summary

Polyesters with protein-like structural complexity have the potential to be used as biomaterials and polymeric materials. By synthesizing enantiomeric omega-hydroxy acids (OHAs) with defined atomic composition, stereochemical configuration, and substituent chemistry, we can build discrete and sequence-defined polyesters, allowing the incorporation of various functional groups at specific locations. Our results demonstrate the possibility of engineering polyesters with structural sophistication comparable to biopolymers like proteins and nucleic acids.