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Influence of ligand substitution on molybdenum catalysts with tridentate Schiff base ligands for the organic solvent-free oxidation of limonene using aqueous TBHP as oxidant
Molecular Catalysis ( IF 4.6 ) Pub Date : 2017-10-07 , DOI: 10.1016/j.mcat.2017.09.033
Weili Wang , Dominique Agustin , Rinaldo Poli

The oxidation of limonene by aqueous TBHP has been analyzed in the presence of molybdenum complexes [MoO2L]2 as catalysts with five different tridentate ligands L in the absence of organic solvents (greener reaction conditions). The ligands are based on a common salicylidene amino(thio)phenolate, SA(T)P, backbone with differences in the coordination sphere (ONO for L = SAP vs. ONS for L = SATP) or in the salicyl moiety functionalization by OH groups for the ONO ligands. The process gives a regioselective endocyclic epoxidation to a kinetically controlled 1:1 mixture of the cis-LimO and trans-LimO epoxides and/or the isomeric diols ax-LimD and eq-LimD by the subsequent ring opening in the presence of water, with a product distribution that depends on the ligand, reaction time and temperature. In combination with control experiments of the cis/trans-LimO ring opening, the investigations demonstrate the catalytic action of the metal complexes in both the epoxidation and the ring opening steps, with the cis-LimO stereospecifically producing the ax-LimD product and the less reactive trans-LimO leading to a 4:3 mixture of ax-LimD and eq-LimD. The ONS system [MoO2(SATP)]2 exhibits the highest catalytic activity in both steps.



中文翻译:

TBHP水溶液作氧化剂对三齿席夫碱配体的钼催化剂对柠檬烯的无溶剂有机氧化氧化的影响

在不存在有机溶剂的情况下,在钼配合物[MoO 2 L] 2作为具有五个不同三齿配体L的催化剂的存在下,对TBHP水溶液中柠檬烯的氧化进行了分析(较绿色的反应条件)。配体基于常见的水杨基亚氨基(硫)酚盐,SA(T)P,在配位域(L = SAP的ONOL = SATP的ONS)或通过OH基团形成的水杨基部分官能度存在差异的主链用于ONO配体。该过程提供了一个区域选择性环内的环氧化的动力学控制1:1混合物的顺式LIMO和反式-LimO环氧化物和/或同分异构的二醇-LimD和EQ-LimD在水的存在下通过随后的开环而形成,其产物分布取决于配体,反应时间和温度。结合/-LimO开环的对照实验,研究表明金属络合物在环氧化和开环步骤中均具有催化作用,其中顺式-LimO立体定向生成ax- LimD产物,而少反应性反式-LimO导致4:3混合物AX- LimD和EQ- LimD。ONS系统[MoO 2(SATP)] 2在两个步骤中均表现出最高的催化活性。

更新日期:2017-10-07
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