A Mild and Chemoselective Reduction of Nitro and Azo Compounds Catalyzed by a Well‐Defined Mo3S4 Cluster Bearing Diamine Ligands
A Mild and Chemoselective Reduction of Nitro and Azo Compounds Catalyzed by a Well‐Defined Mo3S4 Cluster Bearing Diamine Ligands
复制标题
明确的含二胺配体的 Mo3S4 簇催化硝基和偶氮化合物的温和化学选择性还原
DOI：
10.1002/cctc.201500311
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发表时间：
2015
期刊：
影响因子：
4.5
通讯作者：
R. Llusar
中科院分区：
文献类型：
--
作者：
Elena Pedrajas;Iván Sorribes;K. Junge;M. Beller;R. Llusar
在此，我们报告了一种新型的明确的二氨基 Mo3S4 基催化剂体系，用于以硅烷作为还原剂将硝基芳烃和偶氮化合物还原为相应的苯胺。该催化方案提供了一种在温和条件下以良好至优异的产率获取芳香胺的简便途径。值得注意的是，甚至用其他潜在可还原部分官能化的苯胺也能以高选择性获得。通过一锅两步程序将二胺配体与不完整的Mo3S4立方烷型簇核配位，方便地合成了式[Mo3S4Cl3(dmen)3](BF4)（dmen：N,N'-二甲基乙二胺）的新型化学选择性催化剂。 [Mo3S4Cl3(dmen)3]+ 阳离子的晶体结构证实了单一异构体的形成，其中氯原子位于桥接硫原子的反式上，从而提供具有内在主链手性的 C3 对称配合物。多核核磁共振波谱和电喷雾电离质谱技术证明，该结构保留在溶液中。
Herein, we report a novel well‐defined diamino Mo3S4‐based catalyst system for the reduction of nitroarenes and azo compounds to the corresponding anilines with silanes as reducing agents. This catalytic protocol provides a facile route to access aromatic amines under mild conditions in good to excellent yields. Notably, even anilines functionalized with other potentially reducible moieties are obtained with high selectivity. The new chemoselective catalyst of formula [Mo3S4Cl3(dmen)3](BF4) (dmen: N,N′‐dimethylethylenediamine) is conveniently synthesized through coordination of the diamine ligand to the incomplete Mo3S4 cubane‐type cluster core in a one‐pot two‐step procedure. The crystal structure of the [Mo3S4Cl3(dmen)3]+ cation confirms the formation of a single isomer in which the chlorine atom lies trans to the bridging sulfur atom to afford a C3 symmetry complex with intrinsic backbone chirality. The structure is preserved in solution, as evidenced by multinuclear NMR spectroscopy and electrospray‐ionization mass spectrometric techniques.
影响因子：
5.2
作者：
Rahaim, RJ;Maleczka, RE
通讯作者：
Maleczka, RE