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Cationic Single-Unit Monomer Insertion (cSUMI): From Discrete Oligomers to the α-/ω-End and In-Chain Sequence-Regulated Polymers
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-02-01 , DOI: 10.1021/jacs.2c12873 Wei Tao 1, 2 , Wei He 1 , Xuepu Feng 1 , Guoqin Liu 2 , Qiangqiang Shi 2 , Jiajia Tan 2 , Jinming Hu 2 , Sheng Yang 1 , Guhuan Liu 1, 2 , Ronghua Yang 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-02-01 , DOI: 10.1021/jacs.2c12873 Wei Tao 1, 2 , Wei He 1 , Xuepu Feng 1 , Guoqin Liu 2 , Qiangqiang Shi 2 , Jiajia Tan 2 , Jinming Hu 2 , Sheng Yang 1 , Guhuan Liu 1, 2 , Ronghua Yang 1
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Single-unit monomer insertion (SUMI) has become an important strategy for the synthesis of sequence-controlled vinyl polymers due to its strong versatility and high efficiency. However, all reported SUMI processes are based on a free-radical mechanism, resulting in a limited number of monomer types being applicable to SUMI or a limited number of sequences of structural units that SUMI can synthesize. Herein, we developed a novel SUMI based on a cationic mechanism (cSUMI), which operates through a degenerative (similar to radical SUMI) but cationic chain transfer process. By optimizing the chain transfer agent (CTA) and monomer pairs, a high-efficiency cSUMI was achieved for vinyl ether and styrene monomers. Based on this reaction, a range of discrete oligomers containing vinyl ether and styrene moieties, and even α-/ω-end and in-chain sequence-regulated polymers were synthesized, most of which cannot be achieved by radical SUMI. In addition, we explored the application of these sequence-regulated polymers in the preparation of miktoarm star polymers, delivery of photosensitizers, and solubilization of fluorescence probes. The development of SUMI with a new mechanism will certainly broaden the scope of structures and sequences in precise vinyl-based polymers.
中文翻译：
阳离子单元单体插入 (cSUMI)：从离散低聚物到 α-/ω-末端和链内序列调节聚合物
单单元单体插入（SUMI）由于其通用性和高效性已成为合成序列可控乙烯基聚合物的重要策略。然而，所有报道的 SUMI 过程都是基于自由基机制，导致适用于 SUMI 的单体类型数量有限，或者 SUMI 可以合成的结构单元序列数量有限。在此，我们开发了一种基于阳离子机制的新型 SUMI (cSUMI)，它通过退化（类似于自由基 SUMI）但阳离子链转移过程运行。通过优化链转移剂 (CTA) 和单体对，实现了乙烯基醚和苯乙烯单体的高效 cSUMI。基于该反应，一系列含有乙烯基醚和苯乙烯部分的离散低聚物，甚至合成了α-/ω-端和链内序列调控的聚合物，其中大部分是自由基SUMI无法实现的。此外，我们探索了这些序列调控聚合物在制备miktoarm星型聚合物、光敏剂的递送和荧光探针的增溶中的应用。具有新机制的 SUMI 的开发肯定会拓宽精确乙烯基聚合物的结构和序列范围。
更新日期：2023-02-01
中文翻译：
阳离子单元单体插入 (cSUMI)：从离散低聚物到 α-/ω-末端和链内序列调节聚合物
单单元单体插入（SUMI）由于其通用性和高效性已成为合成序列可控乙烯基聚合物的重要策略。然而，所有报道的 SUMI 过程都是基于自由基机制，导致适用于 SUMI 的单体类型数量有限，或者 SUMI 可以合成的结构单元序列数量有限。在此，我们开发了一种基于阳离子机制的新型 SUMI (cSUMI)，它通过退化（类似于自由基 SUMI）但阳离子链转移过程运行。通过优化链转移剂 (CTA) 和单体对，实现了乙烯基醚和苯乙烯单体的高效 cSUMI。基于该反应，一系列含有乙烯基醚和苯乙烯部分的离散低聚物，甚至合成了α-/ω-端和链内序列调控的聚合物，其中大部分是自由基SUMI无法实现的。此外，我们探索了这些序列调控聚合物在制备miktoarm星型聚合物、光敏剂的递送和荧光探针的增溶中的应用。具有新机制的 SUMI 的开发肯定会拓宽精确乙烯基聚合物的结构和序列范围。
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