Asymmetric Ion-Pairing Photoredox Catalysis for Stereoselective Cationic Polymerization under Light Control,Journal of the American Chemical Society

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Asymmetric Ion-Pairing Photoredox Catalysis for Stereoselective Cationic Polymerization under Light Control
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-02-05 , DOI: 10.1021/jacs.3c12694
Zan Yang _{1,

2} , Yun Liao _{1,

2} , Zhengyi Zhang _{1,

2} , Jianxu Chen _{1,

2} , Xun Zhang ₂ , Saihu Liao _{1,

2,

3}

Affiliation

By virtue of noninvasive regulations by light, photocontrolled polymerizations have attracted considerable attention for the precision synthesis of macromolecules. However, a cationic polymerization with simultaneous photocontrol and tacticity-regulation remains elusive so far. Herein, we introduce an asymmetric ion-pairing photoredox catalysis strategy that allows for the development of a stereoselective cationic polymerization with concurrent light regulation for the first time. By employing an ion pair catalyst (PC⁺/*A^–) consisting of a photoredox active cation (PC⁺) and a sterically confined chiral anion (*A^–) to deliver the stereochemical control, the cationic polymerization of vinyl ethers can be achieved with photocontrol and high isotactic selectivity (up to 91% m) at a remarkable low catalyst loading (50 ppm).

中文翻译：

光控下的不对称离子对光氧化还原催化立体选择性阳离子聚合

凭借光的非侵入性调节，光控聚合在大分子的精确合成中引起了广泛的关注。然而，同时具有光控制和立构规整度调节的阳离子聚合迄今为止仍然难以实现。在此，我们引入了一种不对称离子对光氧化还原催化策略，该策略首次允许开发具有并发光调节的立体选择性阳离子聚合。通过采用由光氧化还原活性阳离子（PC ⁺ ）和空间限制的手性阴离子（*A ^– ）组成的离子对催化剂（PC ⁺ /*A ^– ）进行立体化学控制，可以实现乙烯基醚的阳离子聚合具有光控制和高全同立构选择性（高达 91% m ），且催化剂负载量极低（50 ppm）。

更新日期：2024-02-05

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