Combining Orthogonal Chain‐End Deprotections and Thiol–Maleimide Michael Coupling: Engineering Discrete Oligomers by an Iterative Growth Strategy

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 2ⁿ −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=2ⁿ −1) or double exponential dendrimer growth approaches (DP=2 −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.