Ligand-Facilitated Palladium Oxidation Catalysis

超出提供的空间。氧化反应是合成有机化学中最有力的转化之一，因为它们能够增加有机底物的官能度。然而，许多有用的化学计量比氧化剂的高成本和毒性促使人们做出大量努力，开发使用现成的、对环境友好的氧化剂的催化转化。一种新的好氧底物氧化途径是配体促进的钯氧化催化。这些反应不需要氧化还原介体，如氯化铜或苯二酚，在催化循环过程中，钯(0)的氧气偶联氧化。这项拟议的研究将考察配体促进的钯氧化催化剂用于烯烃底物的氧化杂化和碳环化的范围和用途。这项工作将通过实验室开发的新的平行筛选工具和同时详细的催化反应机理表征来促进。在待开发的反应中，有一种新的钯催化的分子间氧化氮转移反应，它使用氧气作为化学计量比的氧化剂。利用氧气作为化学计量比氧化剂的新型催化氧化法在有机化学中具有几乎无限的潜力，特别是在合成天然产物和生物活性分子方面。未来扩展到不对称催化将对药物发现工作产生重大影响。这些反应也是环境友好的，因为它们的副产品(水)是无害的。这些优点，加上氧气的低成本和毒性，将使配体促进的钯氧化催化对工业和学术界的合成有机化学家都很有吸引力。表演网站========================================Section End===========================================

EXCEED THE SPACE PROVIDED. 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. PERFORMANCE SITE ========================================Section End===========================================