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Synthesis of Discrete Oligomers by Sequential PET‐RAFT Single‐Unit Monomer Insertion
Author(s) -
Xu Jiangtao,
Fu Changkui,
Shanmugam Sivaprakash,
Hawker Craig J.,
Moad Graeme,
Boyer Cyrille
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201610223
Subject(s) - raft , monomer , chain transfer , polymer , copolymer , modular design , chemistry , yield (engineering) , oligomer , materials science , polymer chemistry , combinatorial chemistry , radical polymerization , computer science , organic chemistry , metallurgy , operating system
Uniform synthetic polymers with precisely defined molar mass and monomer sequence (primary structure) have many potential high‐value applications. However, a robust and versatile synthetic strategy for these materials remains one of the great challenges in polymer synthesis. Herein we describe proof‐of‐principle experiments for a modular strategy to produce discrete oligomers by a visible‐light‐mediated radical chain process. We utilize the high selectivity provided by photo‐induced electron/energy transfer (PET) activation to develop efficient single unit monomer insertion (SUMI) into reversible addition–fragmentation chain‐transfer (RAFT) agents. A variety of discrete oligomers (single unit species, dimers, and, for the first time, trimers) have been synthesized by sequential SUMI in very high yield under mild reaction conditions. The trimers were used as building blocks for the construction of uniform hexamers and graft copolymers with precisely defined branches.