Unlocking the Potential of Poly(Ortho Ester)s: A General Catalytic Approach to the Synthesis of Surface‐Erodible Materials

Poly(ortho ester)s (POEs) are well‐known for their surface‐eroding properties and hence present unique opportunities for controlled‐release and tissue‐engineering applications. Their development and wide‐spread investigation has, however, been severely limited by challenging synthetic requirements that incorporate unstable intermediates and are therefore highly irreproducible. Herein, the first catalytic method for the synthesis of POEs using air‐ and moisture‐stable vinyl acetal precursors is presented. The synthesis of a range of POE structures is demonstrated, including those that are extremely difficult to achieve by other synthetic methods. Furthermore, application of this chemistry permits efficient installation of functional groups through ortho ester linkages on an aliphatic polycarbonate.