Organocatalyzed Group Transfer Polymerization

In contrast to the conventional group transfer polymerization (GTP) using a catalyst of either an anionic nucleophile or a transition-metal compound, the organocatalyzed GTP has to a great extent improved the living characteristics of the polymerization from the viewpoints of synthesizing structurally well-defined acrylic polymers and constructing defect-free polymer architectures. In this article, we describe the organocatalyzed GTP from a relatively personal perspective to provide our colleagues with a perspicuous and systematic overview on its recent progress as well as a reply to the curiosity of how excellently the organocatalysts have performed in this field. The stated perspectives of this review mainly cover five aspects, in terms of the assessment of the livingness of the polymerization, limit and scope of applicable monomers, mechanistic studies, control of the polymer structure, and a new GTP methodology involving the use of tris(pentafluorophenyl)borane and hydrosilane.