Flavin-Functionalized Gold Nanoparticles as an Efficient Catalyst for Aerobic Organic Transformations
Flavin-Functionalized Gold Nanoparticles as an Efficient Catalyst for Aerobic Organic Transformations
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黄素功能化金纳米颗粒作为有氧有机转化的有效催化剂
DOI：
10.1002/cctc.201402619
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
and Takeshi Naota
中科院分区：
文献类型：
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作者：
Yasushi Imada;Motonari Ohsaki;Mikiko Noguchi;Takatoshi Maeda;Misa Fujiki;Soichiro Kawamorita;Naruyoshi Komiya;and Takeshi Naota
合成了单分子层保护的黄素功能化的金簇，并研究了它们在有氧有机转化中的催化活性。金纳米粒子与5-乙基-3-（8-硫代辛基）lumiflavinium高氯酸盐作为一个有效的催化剂，在有氧氧化有机硫化物相应的亚砜处理后，在室温和常压下在氧气中。使用催化量的金纳米颗粒与3-（8-硫代辛基）荧光黄素，可以在室温、大气压力和空气中用肼进行各种烯烃的二酰亚胺还原，产物烷烃的产率比使用非负载型3-甲基荧光黄素催化剂更高在相同的条件下。动力学研究表明，单层保护的金簇催化的反应进行得比那些与非负载型催化剂在整个底物浓度范围内的烯烃加氢和在较低的底物浓度的磺基氧化更快。通过假设Michaelis-Menten-type机制来合理化这种积极效应，其中将底物特异性地包含在酶样反应腔中是负载型黄素催化剂高效率的关键因素。
Monolayer‐protected gold clusters functionalized with synthetic flavins were synthesized and their catalytic activity in aerobic organic transformations investigated. Gold nanoparticles with 5‐ethyl‐3‐(8‐thiooctyl)lumiflavinium perchlorate acts as an efficient catalyst for the aerobic oxidation of organic sulfides to the corresponding sulfoxides upon treatment with hydrazine at room temperature and under atmospheric pressure in oxygen. With a catalytic amount of gold nanoparticles with 3‐(8‐thiooctyl)lumiflavin, diimide reduction of various olefins can be performed with hydrazine at room temperature under atmospheric pressure in air with greater yields of product alkanes than with non‐supported 3‐methyllumiflavin catalyst under the same conditions. Kinetic studies revealed that the monolayer‐protected gold cluster‐catalyzed reactions proceeded faster than those with non‐supported catalysts over the full substrate concentration range for the hydrogenation of olefins and at lower substrate concentrations for sulfoxidation. This positive effect was rationalized by assuming a Michaelis–Menten‐type mechanism in which the specific inclusion of substrates into the enzyme‐like reaction cavities was a key factor in the high efficiency of the supported flavin catalysts.