Alloying Gold with Copper Makes for a Highly Selective Visible-Light Photocatalyst for the Reduction of Nitroaromatics to Anilines,ACS Catalysis

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Alloying Gold with Copper Makes for a Highly Selective Visible-Light Photocatalyst for the Reduction of Nitroaromatics to Anilines
ACS Catalysis ( IF 11.3 ) Pub Date : 2016-02-12 00:00:00 , DOI: 10.1021/acscatal.5b02643
Qi Xiao ₁ , Sarina Sarina ₁ , Eric R. Waclawik ₁ , Jianfeng Jia ₂ , Jin Chang _{1,

3} , James D. Riches ₄ , Haishun Wu ₂ , Zhanfeng Zheng ₅ , Huaiyong Zhu ₁

Affiliation

Finely control of product selectivity is an essential issue in organic chemical production. In the synthesis of functionalized anilines via reduction of the corresponding nitroarenes, the challenge is to selectively reduce only the nitro group in the presence of other reducible functional groups in nitroarene molecules at a high reaction rate. Normally, the nitroarene is reduced stepwise through a series of intermediates that remain as byproducts, increasing the aniline synthesis cost. Here we report that alloying small amounts of copper into gold nanoparticles can alter the reaction pathway of the catalytic reduction under visible-light irradiation at ambient temperature, allowing nitroaromatics to be transformed directly to anilines in a highly selective manner. The reasons for the high efficiency of the photocatalytic reduction under these comparatively benign conditions as well as the light-excited reaction mechanisms are discussed. This photocatalytic process avoids byproducts, exhibits a high reaction rate and excellent substituent tolerance, and can be used for the synthesis of many useful functionalized anilines under environmentally benign conditions. Switching of the reaction pathway simply by tailoring the bimetallic alloy NPs of the photocatalysts is effective for engineering of product chemoselectivity.

中文翻译：

铜与金形成合金可产生高选择性可见光光催化剂，以将硝基芳烃还原为苯胺

精细控制产品的选择性是有机化学生产中必不可少的问题。在通过还原相应的硝基芳烃来合成官能化的苯胺中，挑战是在硝基芳烃分子中以高反应速率存在的其他可还原的官能团的存在下，仅选择性地还原硝基。通常，通过一系列作为副产物保留的中间体逐步还原硝基芳烃，从而增加了苯胺的合成成本。在这里，我们报道了将少量的铜合金化成金纳米颗粒可以改变环境温度下可见光照射下催化还原的反应途径，从而使硝基芳族化合物以高度选择性的方式直接转化为苯胺。讨论了在这些相对温和的条件下光催化还原效率高的原因以及光激发的反应机理。该光催化过程避免了副产物，表现出高反应速率和优异的取代基耐受性，并且可用于在环境良好的条件下合成许多有用的官能化苯胺。简单地通过调整光催化剂的双金属合金NPs来切换反应路径对于设计产品的化学选择性是有效的。并可以在环境良好的条件下用于合成许多有用的功能化苯胺。仅通过定制光催化剂的双金属合金NPs即可切换反应途径，对设计产品的化学选择性非常有效。并可以在环境良好的条件下用于合成许多有用的功能化苯胺。仅通过定制光催化剂的双金属合金NPs即可切换反应途径，对设计产品的化学选择性非常有效。

更新日期：2016-02-12

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