Active Cp*Iridium(III) Complex with ortho-Hydroxyl Group Functionalized Bipyridine Ligand Containing an Electron-Donating Group for the Production of Diketone from 5-HMF
Active Cp*Iridium(III) Complex with ortho-Hydroxyl Group Functionalized Bipyridine Ligand Containing an Electron-Donating Group for the Production of Diketone from 5-HMF
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DOI：
10.1021/acscatal.6b00826
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发表时间：
2016-05
期刊：
影响因子：
12.9
通讯作者：
Zhanwei Xu;Peifang Yan;Huixiang Li;Kairui Liu;Xiumei Liu;Songyan Jia;Z. Conrad Zhang
中科院分区：
文献类型：
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作者：
Zhanwei Xu;Peifang Yan;Huixiang Li;Kairui Liu;Xiumei Liu;Songyan Jia;Z. Conrad Zhang
二酮是有机合成中普遍存在的嵌段化合物。该工作显示了用于通过氢化生物基平台化学品5-羟甲基糠醛（5-HMF）来生产二酮1-羟基己烷-2，5-二酮（HHD）的高活性催化剂。合成了含邻位羟基功能化联吡啶配体的半夹心Cp*Ir配合物，发现其在酸性水中对该反应表现出非常高的催化活性.当Cp*Ir配合物的联吡啶配体被给电子基团修饰时，HHD形成速率进一步增加。同时具有二甲氨基和邻位羟基的联吡啶配体在H2和甲酸作用下的HHD形成转换频率（TOF）分别为31 560 h-1和6140 h-1，分别是文献报道的最佳结果的180倍和3 000倍.
Diketones are ubiquitous blocks for organic synthesis. This work shows a highly active catalyst for the production of diketone 1-hydroxyhexane-2,5-dione (HHD) by hydrogenation of 5-hydroxymethylfurfural (5-HMF), a biobased platform chemical. Half-sandwich Cp*Ir complexes with ortho-hydroxyl group functionalized bipyridine ligands were synthesized and found to exhibit remarkably high catalytic activity for this reaction in acidic water. The HHD formation rate was further increased when the bipyridine ligands of Cp*Ir complexes were modified by an electron-donating group. A bipyridine ligand with both dimethylamino and ortho-hydroxyl groups achieved a HHD formation turnover frequency (TOF) of 31 560 h–1 by H2 and a TOF of 6140 h–1 by formic acid, representing 180-fold and 3 000-fold over the activities of the best reported results, respectively.