The synthesis of medium- and short-chain aliphatic polyethers is industrially limited to the ring-opening polymerization of cyclic ethers with a high ring strain, such as oxiranes, oxetanes, or tetrahydrofuran. This structural limitation can be overcome by the gallium bromide catalyzed reduction of different polyesters into their corresponding polyethers. Herein, the scope of applicable polyesters is broadened, while the influence of the polyester structure on the reduction system is examined. The reactivity as well as side reactions, i.e., overreduction leading to chain cleavage, are shown to depend on the distance of the ester groups in the repeating unit of the polyester. Two different reducing agents, namely triethylsilane and 1,1,3,3-tetramethyldisiloxane, are studied and compared in terms of reactivity and work-up procedures, showing advantages and disadvantages depending on the reduced polyester properties. The reaction conditions are optimized and the reduction can be scaled-up to 60 g polyester. All products are thoroughly characterized
