Ligand-Facilitated Palladium Oxidation Catalysis

配体促进的钯氧化催化

基本信息

批准号：
7159330
负责人：
Shannon S Stahl
金额：
$ 22.27万
依托单位：
UNIVERSITY OF WISCONSIN-MADISON
依托单位国家：
美国
项目类别：
财政年份：
2003
资助国家：
美国
起止时间：
2003-01-01 至 2008-06-30
项目状态：
已结题

项目摘要

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.

氧化反应是合成有机化学中最强大的转化之一，因为它们增加有机底物功能的能力。但是，高成本和毒性许多有用的化学计量氧化剂已经促使大力发展催化转化这种易于使用和环境良性氧化剂。有氧底物的新型途径氧化是配体辅助钯氧化催化。这些反应不需要氧化还原介质作为催化期间钯（0）的二氧化偶联氧化的铜（LL）氯化物或苯二喹酮周转。拟议的研究将检查配体辅助钯氧化的范围和实用性烯烃底物的氧化杂异的和碳环孔化的催化。这项工作将由实验室中开发的新的并行筛选工具以及同时详细的机械表征催化反应。在要开发的反应中有新的钯催化的分子间氧化氮转移反应采用二氧化物作为化学计量氧化剂。采用二氧化剂作为化学计量氧化剂的新催化氧化几乎无限有机化学的潜力，特别是用于合成天然产物和生物活性的分子。未来扩展到不对称催化将对药物发现产生重大影响努力。由于它们的良性副产品（水），这些反应也对环境友好。这些资产，以及二氧化物的低成本和毒性，将使配体促钯氧化催化对工业和学术界的合成有机化学家的吸引力非常有吸引力。