Shuangyan Hu, Junpeng Zhao, Guangzhao Zhang, Helmut Schlaad

• In virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashionIn virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashion different polymer chains are covalently attached to each other within the macromolecule) and functionality (position and amount of functional groups that endow the entire macromolecule with specific chemical, physico-chemical or biological properties). (C) 2017 Published by Elsevier B.V.…