Multi‐Site Organoboron Catalysts Enable Sequence‐Regulated Terpolymerization of Epoxides, CO 2 , and β ‐Propiolactone via Intermolecular Chain Shuttling

ring-opening copolymerization (ROCOP), yielding PC-b-P3HP; ii) Boron centers kinetically suppressed ROP but increased ROCOP efficiency; iii) Mixed 1 and 2 catalysts enabled intermolecular chain shuttling, synthesizing gradient PC-grad-P3HP terpolymers; and iv) Terpolymer compositions modulated thermal properties from amorphous to crystalline. This work establishes the first metal-free, chain-shuttling platform for sequence-regulated PC-PHA terpolymers, extending the scope of programmable biodegradable materials beyond metal-catalyzed systems.