钯催化叔丁基过氧化氢介导的喹啉-2-噁唑啉配体促进的烯烃瓦克型氧化反应的机理。
On the mechanism of the palladium-catalyzed tert-butylhydroperoxide-mediated Wacker-type oxidation of alkenes using quinoline-2-oxazoline ligands.
机构信息
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA.
出版信息
J Am Chem Soc. 2011 Jun 1;133(21):8317-25. doi: 10.1021/ja2017043. Epub 2011 May 9.
Abstract
The mechanism of the tert-butylhydroperoxide-mediated, Pd(Quinox)-catalyzed Wacker-type oxidation was investigated to evaluate the hypothesis that a selective catalyst-controlled oxidation could be achieved by rendering the palladium coordinatively saturated using a bidentate amine ligand. The unique role of the Quinox ligand framework was probed via systematic ligand modifications. The modified ligands were evaluated through quantitative Hammett analysis, which supports a "push-pull" relationship between the electronically asymmetric quinoline and oxazoline ligand modules.
摘要
研究了叔丁基过氧化物介导的、Pd(Quinox)-催化的 Wacker 型氧化反应的机理，以评估以下假设：通过使用双齿胺配体使钯配位饱和，可以实现选择性催化剂控制的氧化。通过系统的配体修饰来探究 Quinox 配体骨架的独特作用。通过定量的 Hammett 分析评估了修饰后的配体，该分析支持电子不对称的喹啉和恶唑啉配体模块之间存在“推-拉”关系。
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