Cooperative Catalysis by Boronic Acid-Amine Bifunctionalized Polyacrylonitrile Fibers in Henry Reaction,ACS Catalysis

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Cooperative Catalysis by Boronic Acid-Amine Bifunctionalized Polyacrylonitrile Fibers in Henry Reaction
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-05-26 , DOI: 10.1021/acscatal.3c00906
Haotian Zhang ₁ , Haonan Zhang ₁ , Huimin Du ₁ , Jian Xiao ₁ , Minli Tao _{1,

2} , Ning Ma _{1,

2} , Wenqin Zhang _{1,

2}

Affiliation

The acid–base pairing and fabrication method was herein employed to construct acid–base bifunctional heterogeneous catalysts. The boronic acid group was introduced into primary amine-functionalized polyacrylonitrile fiber (PAN_EAF) via amide bond formation to fabricate boronic acid-amine bifunctional PANFs as recyclable heterogeneous catalysts by using the amino N atoms of PAN_EAF as anchoring points. The so-obtained fiber catalysts PAN_EA–BA1F and PAN_EA–BA2F containing boronic acid groups attached on benzene and pyridine rings, respectively, were employed in the Henry reactions of aryl aldehydes with nitromethane. Catalytic investigations showed that their performance had great correlation with the change of boronic acid. PAN_EA–BA2F exhibited a higher substrate selectivity than PAN_EA–BA1F, and only the benzaldehydes with hydroxy, dimethylamino, and amide groups were reactive, which showed preliminary substrate specificity like enzyme catalysis. The in situ investigation with cyclododecane as solvent by Raman and Fourier transform infrared spectroscopy (FT-IR) analysis was conducted to clarify the catalytic difference. Moreover, the uncommon reverse reactivity order of benzaldehydes in PAN_EA–BA1F-catalyzed condensation was explained.

中文翻译：

硼酸-胺双功能化聚丙烯腈纤维协同催化亨利反应

本文采用酸碱配对和制备方法构建酸碱双功能多相催化剂。通过形成酰胺键将硼酸基团引入伯胺官能化聚丙烯腈纤维（PAN _EA F）中，以 PAN _EA F 的氨基 N 原子为锚定点，制备硼酸-胺双官能 PANF 作为可回收的多相催化剂。如此获得的分别含有连接在苯环和吡啶环上的硼酸基团的纤维催化剂PAN _EA-BA1 F和PAN _{EA-BA2 F，分别用于芳基醛与硝基甲烷的亨利反应。}催化研究表明其性能与硼酸的变化有很大的相关性。平底锅_{EA-BA2 F 表现出比 PAN}_EA-BA1 F更高的底物选择性，并且只有具有羟基、二甲氨基和酰胺基团的苯甲醛才具有反应性，初步表现出类似酶催化的底物特异性。以环十二烷为溶剂，通过拉曼和傅里叶变换红外光谱（FT-IR）分析进行原位研究，以阐明催化差异。此外，还解释了苯甲醛在 PAN _EA-BA1 F 催化缩合反应中不常见的逆反应顺序。

更新日期：2023-05-26

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