Gold(I) Catalysis at Extreme Concentrations Inside Self-Assembled Nanospheres
Gold(I) Catalysis at Extreme Concentrations Inside Self-Assembled Nanospheres
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DOI：
10.1002/anie.201406415
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发表时间：
2014-12-01
影响因子：
16.6
通讯作者：
Reek, Joost N. H.
中科院分区：
文献类型：
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作者：
Gramage-Doria, Rafael;Hessels, Joeri;Reek, Joost N. H.
均相过渡金属催化是可持续制备有价值化学品的关键技术。催化剂浓度通常保持尽可能低，典型地在mm或mm水平，并且由于溶解度问题和固有的不利的催化剂/底物比，几乎不利用高催化剂浓度的效果。在本文中，报道了自组装策略，其导致局部催化剂浓度范围从0.05M至1.1M，在明确定义的纳米球内，而溶液中的总催化剂浓度保持在常规的mm水平。我们公开了只有在该高浓度下，氯化金（I）才是反应性的，并且在分子内C-O和C-C键形成环化反应中显示出高选择性。
Homogeneous transition-metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mm or mm levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05M to 1.1M, inside well-defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mm levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular C-O and C-C bond-forming cyclization reactions.