Organic Transformations with h2-Arene Complexes of Rhenium

铼的 h2-芳烃配合物的有机转化

• 批准号: 0111558
• 负责人: Walter Harman
• 金额: $ 36.9万
• 依托单位: University of Virginia Main Campus
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-09-01 至 2004-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0111558&HistoricalAwards=false
• 关键词: Organic; Transformations; h2; Arene; Complexes

With the support of the Organic and Macromolecular Chemistry Program, Professor W. Dean Harman, of the Department of Chemistry at the University of Virginia, is studying organic transformations using eta-2 arene complexes of rhenium. Through the selective and reversible binding of arenes or polyaromatic hydrocarbons through dihapto coordination to a transition metal, their reactivity toward electrophiles is enhanced. Reactive intermediates (e.g., arenium and allyl cations) are stabilized, facilitating the assembly of polycyclic structures. In addition, metal coordination directs the stereochemistry of various chemical transformations and protects the coordination site for additional transformations. While dihapto coordination of arenes has previously been limited to pentaammineosmium(II) complexes, Professor Harman is developing a new class of rhenium(I)-based dearomatization agents.Aromatic compounds (e.g., benzene, toluene) represent one of the most readily available classes of compounds for elaboration into more complex molecular structures. However, their unique properties place some limitations on the chemical reactions available for their elaboration. Professor W. Dean Harman, of the Department of Chemistry at the University of Virginia, with the support of the Organic and Macromolecular Chemistry Program, is developing unique metal-based reagents which allow for the dramatic alteration of the reactivity of aromatic compounds. Through his studies, new methods are being developed allowing the facile and selective conversion of these readily available starting materials to compounds of potential significance in their own right or as intermediates in the synthesis of pharmaceuticals and other fine chemical products.

在有机和高分子化学项目的支持下，W。弗吉尼亚大学化学系的迪安·哈曼（Dean Harman）正在研究使用β-2芳烃配合物的有机转化。通过芳烃或多环芳烃通过双配位与过渡金属的选择性和可逆结合，增强了它们对亲电体的反应性。反应性中间体（例如，阳离子和烯丙基阳离子）是稳定的，促进了多环结构的组装。此外，金属配位指导各种化学转化的立体化学，并保护配位位点用于其他转化。虽然芳烃的双hapto配位以前仅限于五胺锇（II）络合物，但Harman教授正在开发一类新的基于五胺锇（I）的脱芳构化剂。苯、甲苯）代表了用于加工成更复杂分子结构的最容易获得的一类化合物。然而，其独特的性质对可用于其加工的化学反应施加了一些限制。教授W。弗吉尼亚大学化学系的Dean Harman在有机和大分子化学项目的支持下，正在开发独特的金属基试剂，这些试剂可以显著改变芳香族化合物的反应性。通过他的研究，正在开发新的方法，允许这些容易获得的起始材料简单和选择性地转化为具有潜在意义的化合物，或者作为药物和其他精细化学产品合成的中间体。