Ligand-Facilitated Palladium Oxidation Catalysis

氧化反应是合成有机化学中最强大的转化之一，因为 提高有机底物功能的能力。然而，其高昂的成本和毒性 许多有用的化学计量比氧化剂已经推动了开发催化转化的大量努力 使用容易获得的、对环境无害的氧化剂。一种新的好氧基质生成途径 氧化是配体促进的钯氧化催化作用。这些反应不需要这样的氧化还原调节剂 氯化铜或苯二酚催化氧化钯(0)的研究 营业额。 拟议的研究将考察配体促进的钯氧化的范围和用途。 烯烃底物氧化杂化和碳环化的催化作用。这项工作将由 在实验室开发的新的并行筛选工具和同时详细的机械表征 催化反应。有待开发的反应包括新的钯催化的分子间反应。 使用氧气作为化学计量比氧化剂的氧化氮转移反应。 使用氧气作为化学计量比氧化剂的新型催化氧化反应几乎没有限制 在有机化学方面的潜力，特别是在合成天然产物和生物活性方面的潜力 分子。未来对不对称催化的扩展将对药物发现产生重大影响 努力。这些反应也是环境友好的，因为它们的副产品(水)是无害的。这些 资产，再加上氧气的低成本和毒性，将使配体促进钯的氧化 催化对工业界和学术界的合成有机化学家都很有吸引力。

Oxidation reactions are among the most powerful transformations in synthetic organic chemistry because of their ability to increase the functionality of organic substrates. However, the high costs and toxicity of many useful stoichiometric oxidants have prompted substantial effort to develop catalytic transformations that employ readily available and environmentally benign oxidants. A novel pathway for aerobic substrate oxidation is ligand-facilitated palladium oxidation catalysis. These reactions require no redox mediators such as copper(ll) chloride or benzoquinone for dioxygen-coupled oxidation of palladium(0) during catalytic turnover. The proposed research will examine the scope and utility of ligand-facilitated palladium oxidation catalysis for the oxidative hetero- and carbocyclization of olefinic substrates. This work will be facilitated by new parallel screening tools developed in the lab and simultaneous detailed mechanistic characterization of the catalytic reactions. Among the reactions to be developed are new palladium-catalyzed intermolecular oxidative nitrogen-transfer reactions that employ dioxygen as the stoichiometric oxidant. New catalytic oxidations that employ dioxygen as the stoichiometric oxidant have almost unlimited potential in organic chemistry, particularly for the synthesis of natural products and biologically active molecules. Future expansions into asymmetric catalysis would have a significant impact on drug discovery efforts. These reactions are environmentally friendly as well due to their benign by-products (water). These assets, along with the low cost and toxicity of dioxygen, will make ligand-facilitated palladium oxidation catalysis quite attractive to synthetic organic chemists in industry as well as those in academia.