Efficient Transformation of Polymer Main Chain Catalyzed by Macrocycle Metal Complexes via Pseudorotaxane Intermediate

被引：2

作者：

Takata, Toshikazu ^{[1
,2
,3
]}

Yamamoto, Koji ^{[1
,2
,4
]}

Higuchi, Kazuki ^{[2
]}

Ogawa, Masahiro ^{[2
]}

Kawasaki, Ayumi ^{[2
]}

Mizuno, Shunya ^{[2
]}

Iwasaki, Hikaru ^{[2
]}

Nagashima, Masaki ^{[2
]}

Hayashi, Yoshihiro ^{[2
,5
,6
]}

Kawauchi, Susumu ^{[2
,7
]}

Nakazono, Kazuko ^{[1
,2
]}

Koyama, Yasuhito ^{[8
]}

机构：

[1] Tokyo Inst Technol, Sch Mat & Chem Technol, 4259 Nagatsuta Cho,Midori Ku, Yokohama 2268503, Japan

[2] Tokyo Inst Technol, Dept Chem Sci & Engn, 2-12-1 Ookayama, Tokyo 1528552, Japan

[3] Hiroshima Univ, Grad Sch Adv Sci & Engn, 1-4-1 Kagamiyama, Hiroshima, Hiroshima 7398527, Japan

[4] Shujitsu Univ, Dept Pharmaceut Sci, 1-6-1 Nishigawara, Okayama 7038516, Japan

[5] Res Org Informat & Syst, Inst Stat Math, Tachikawa, Tokyo 1908562, Japan

[6] Grad Univ Adv Studies, SOKENDAI, Tachikawa, Tokyo 1908562, Japan

[7] Tokyo Tech Acad Convergence Mat & Informat TAC MI, Tokyo Inst Technol, Tokyo 1528550, Japan

[8] Toyama Prefecture Univ, Dept Pharmaceut Engn, 5180 Kurokawa, Imizu, Toyama 9390398, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 24期

关键词：

Intermolecular Hydrosilylation; Intramolecular Hydroamination; Macrocycle Metal Complex; Polymer Reaction; Pseudorotaxane Intermediate; CRYSTAL-STRUCTURE; MECHANISM; HYDROAMINATION;

D O I：

10.1002/anie.202303494

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Post-synthesis modification of polymers streamlines the synthesis of functionalized polymers, but is often incomplete due to the negative polymer effects. Developing efficient polymer reactions in artificial systems thus represents a long-standing objective in the fields of polymer and material science. Here, we show unprecedented macrocycle-metal-complex-catalyzed systems for efficient polymer reaction that result in 100 % transformation of the main chain functional groups presumably via a processive mode reaction. The complete polymer reactions were confirmed in not only intramolecular reaction (hydroamination) but also intermolecular reaction (hydrosilylation) by using Pd- and Pt-macrocycle-catalyzed systems. The most fascinating feature of the both reactions is that higher-molecular-weight polymers reach completion faster. Various studies suggested that the reactions occur in the catalyst cavity via the formation of a supramolecular complex between the macrocycle catalyst and polymer substrate like pseudorotaxane, which should be of characteristic of the efficient polymer reactions progressing in a processive mode.

引用

页数：5

共 28 条

[1] 50th Anniversary Perspective: Polymer Functionalization [J].