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Combining Orthogonal Chain‐End Deprotections and Thiol–Maleimide Michael Coupling: Engineering Discrete Oligomers by an Iterative Growth Strategy
Author(s) -
Huang Zhihao,
Zhao Junfei,
Wang Zimu,
Meng Fanying,
Ding Kunshan,
Pan Xiangqiang,
Zhou Nianchen,
Li Xiaopeng,
Zhang Zhengbiao,
Zhu Xiulin
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706522
Subject(s) - maleimide , oligomer , thiol , macromolecule , polymerization , coupling (piping) , materials science , polymer chemistry , bifunctional , topology (electrical circuits) , chemistry , polymer , mathematics , organic chemistry , composite material , combinatorics , biochemistry , catalysis
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 n −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 n −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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