Orthogonal maleimide and thiol deprotections were combined with thiol-maleimide coupling to synthesize discrete oligomers/macromolecules on a gram scale with molecular weights up to 27.4 kDa (128mer, 7.9 g) using an iterative exponential growth strategy with a degree of polymerization (DP) of 2 -1. Using the same chemistry, a "readable" sequence-defined oligomer and a discrete cyclic topology were also created. Furthermore, uniform dendrons were fabricated using sequential growth (DP=2 -1) or double exponential dendrimer growth approaches (DP=22n -1) with significantly accelerated growth rates. A versatile, efficient, and metal-free method for construction of discrete oligomers with tailored structures and a high growth rate would greatly facilitate research into the structure-property relationships of sophisticated polymeric materials.

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We highlight recent work from the advent of zero-valent metal-mediated RDRP looking at advances in its components and the synthesis of well-defined polymers.

A straightforward approach for the synthesis of cyclic polymers in a one-pot reaction.

A facile approach to synthesize GMA polymers using Fe(0)/RAFT agent mediated control radical polymerization.