Zr(OH)
<sub>4</sub>
‐Catalyzed Controllable Selective Oxidation of Anilines to Azoxybenzenes, Azobenzenes and Nitrosobenzenes
作者:Jiaheng Qin、Yu Long、Fangkun Sun、Pan‐Pan Zhou、Wei David Wang、Nan Luo、Jiantai Ma
DOI:10.1002/anie.202112907
日期:2022.1.10
Zr(OH)4 can catalyze the selective oxidation of anilines to azoxybenzenes, symmetric/unsymmetric azobenzenes and nitrosobenzenes for a wide range of substrates. Control experiments and DFT calculations reveal that the activation of H2O2 and O2 can be attributed to the bridging hydroxyl and terminal hydroxyl groups of Zr(OH)4, respectively.
Zr(OH) 4可以催化苯胺选择性氧化为偶氮苯、对称/不对称偶氮苯和亚硝基苯,适用于多种底物。对照实验和 DFT 计算表明,H 2 O 2和 O 2的活化可分别归因于 Zr(OH) 4的桥接羟基和末端羟基。
Selective Oxidation of Anilines to Azobenzenes and Azoxybenzenes by a Molecular Mo Oxide Catalyst
molybdenum oxide compound, [N(C4H9)4]2[Mo6O19] (1), catalyzed selective oxidation of anilines with hydrogen peroxide as green oxidant. The oxidation of anilines can be realized in a fully selectively fashion to afford various symmetric/asymmetric azobenzene and azoxybenzene compounds, respectively, by changing additive and solvent, avoiding the use of stoichiometric metal oxidants. Preliminary mechanistic
在医药和工业应用中起重要作用的芳族偶氮化合物在合成中仍然面临巨大挑战。在此,我们报道了一种氧化钼化合物[N(C 4 H 9)4 ] 2 [Mo 6 O 19 ](1),用过氧化氢作为绿色氧化剂催化苯胺的选择性氧化。苯胺的氧化可以完全选择性地实现,通过改变添加剂和溶剂避免使用化学计量的金属氧化剂,从而分别提供各种对称/不对称的偶氮苯和and氧基苯化合物。初步的机理研究表明,高活性的反应性和难以捉摸的钼亚胺配合物是中间的。