Pathak Debabrat, Khatioda Rajiv, Sharma Himanshu, Guha Ankur K, Saikia Lakshi, Sarma Bipul
Department of Chemical Sciences, Tezpur University, Napaam, Tezpur 784028, Assam, India.
School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, Guangdong, China.
ACS Appl Mater Interfaces. 2021 Apr 7;13(13):15353-15365. doi: 10.1021/acsami.1c03158. Epub 2021 Mar 25.
Oxidative cleavage of styrene C═C double bond is accomplished by employing a nitrogen-rich triazine-based microporous organic polymer as an organocatalyst. We report this regioselective reaction as first of its kind with no metal add-ons to afford benzaldehydes up to 92% selectivity via an unusual Wacker-type C═C bond cleavage. Such a reaction pathway is generally observed in the presence of a metal catalyst. This polymer further shows high catalytic efficiency in an anaerobic oxidation reaction of benzyl alcohols into benzaldehydes. The reaction is mediated by a base via the generation of hydride ions. This study is supported by experiments and computational analyses for a free-radical transformation reaction of oxidative C═C bond cleavage of styrenes and a hydride elimination mechanism for the anaerobic oxidation reaction. Essentially, the study unveils protruding applications of metal-free nitrogen-rich porous polymers in organic transformation reactions.
通过使用富含氮的三嗪基微孔有机聚合物作为有机催化剂，实现了苯乙烯碳碳双键的氧化裂解。我们报道了这种区域选择性反应，这是首例此类反应，无需添加金属，通过不寻常的瓦克型碳碳键裂解，可选择性地生成高达92%的苯甲醛。这种反应途径通常是在金属催化剂存在下观察到的。这种聚合物在苄醇厌氧氧化生成苯甲醛的反应中还表现出高催化效率。该反应由碱通过氢负离子的产生介导。本研究得到了苯乙烯氧化碳碳键裂解的自由基转化反应以及厌氧氧化反应的氢化物消除机理的实验和计算分析的支持。本质上，该研究揭示了无金属富含氮的多孔聚合物在有机转化反应中的突出应用。
