Synthetic and mechanistic investigations on manganese corrole-catalyzed oxidation of sulfides with iodobenzene diacetate
Synthetic and mechanistic investigations on manganese corrole-catalyzed oxidation of sulfides with iodobenzene diacetate
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DOI：
10.1016/j.ica.2018.11.048
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发表时间：
2019-03
影响因子：
2.8
通讯作者：
Davis Ranburger;Ben E. Willis;Benjamin Kash;H. Jeddi;C. Alcantar;Rui Zhang
中科院分区：
文献类型：
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作者：
Davis Ranburger;Ben E. Willis;Benjamin Kash;H. Jeddi;C. Alcantar;Rui Zhang
在少量水的存在下，以二乙酸碘苯[PhI（OAc）2]为温和的氧源，锰的咔咯配合物催化有机硫化物氧化成亚砜。各种取代的茴香硫醚可以有效地氧化为亚砜，具有定量转化率（高达2500吨）和优异的亚砜选择性。研究了催化剂的催化效果，包括中心锰的氧化态和配体，并显示出显着的影响，催化亚砜化。先前已知的高价锰（V）-氧代可罗莱化学生成和动力学研究中的苯硫醚底物的氧化。竞争结果表明，锰金属的氧化态是至关重要的控制活性氧化剂形式的性质，显着影响其催化活性。
Manganese corrole complexes catalyze the efficient oxidation of organic sulfides to sulfoxides with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source in the presence of small amounts of water. Various substituted thioanisoles can be efficiently oxidized to sulfoxides with quantitative conversions (up to 2500 TONs) and excellent selectivies for sulfoxides. The catalyst effects, including the corrole ligands and oxidation states of the central manganese, were investigated, and showed a significant impact on the catalytic sulfoxidations. The previously known high-valent manganese(V)-oxo corroles were chemically generated and kinetically studied in the oxidation of thioanisole substrates. The competition results suggested the oxidation state of manganese metal is crucial to control the nature of active oxidant forms that significantly affected their catalytic activity.