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

Abstract

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.