Synthesis and Reactivity of Substituted Cyclopentadienylmetals

取代环戊二烯基金属的合成和反应活性

• 批准号: 0091770
• 负责人: Ronald Halterman
• 金额: $ 32.4万
• 依托单位: University of Oklahoma Norman Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-05-01 至 2005-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0091770&HistoricalAwards=false
• 关键词: Synthesis; Reactivity; Substituted; Cyclopentadienylmetals

The proposed research addresses several main goals within the context of cyclopentadienyl metal complexes. Efficient synthetic methods will be developed for the synthesis of known cyclopentadienyl ligands and complexes as well as new chiral cyclopentadienyl and indenyl metal complexes. Chiral indenyl and cyclopentadienyl ligands bearing tethered donor ligands will be synthesized and coordinated to metals. Finally, the activity of the chiral complexes in enantioselective carbon-carbon and carbon-hydrogen bond forming reactions will be explored. Ligand syntheses will be effected through exploitation of the cross-coupling reactions of 2-bromoindenyl complexes, the ring closing metathesis reaction (yielding indenes from phenyldienes), and the chromium(II)/nickel carbonyl addition method to convert bromoarenes or bromoalkenes and ketones or aldehydes to substituted indenes and cyclopentadienes.With this award, the Organic Synthesis Program is supporting the research of Professor Ronald L. Halterman of the Department of Chemistry and Biochemistry at the University of Oklahoma. Professor Halterman's studies are directed toward the synthesis of new catalysts designed to effect the formation of carbon-carbon and carbon-hydrogen bonds with precise control over the detailed three-dimensional structure ("stereochemistry") of the products. These studies, focused largely on the synthesis of new stereochemically defined "scaffolds" to support catalytically active metal centers, are of direct relevance to the synthesis of pharmaceuticals and polymeric materials, endeavors in which the need for stereochemical control continues to grow.

拟议的研究解决了几个主要目标范围内的金属配合物。有效的合成方法将被开发用于合成已知的手性茚基配体和配合物以及新的手性茚基和茚基金属配合物。手性茚基配体和手性茚基配体将被合成并与金属配位。最后，将探讨手性配合物在不对称选择性碳-碳键和碳-氢键形成反应中的活性。通过利用2-溴茚基络合物的交叉偶联反应、闭环复分解反应（由苯二烯生成茚）以及铬（II）/羰基镍加成法将溴代芳烃或溴代烯烃和酮或醛转化为取代的茚和环戊二烯来实现配体合成。有了这个奖项，有机合成计划支持罗纳德L教授的研究。俄克拉荷马州大学化学和生物化学系的Halterman说。Halterman教授的研究方向是合成新的催化剂，旨在影响碳-碳和碳-氢键的形成，并精确控制产品的详细三维结构（“立体化学”）。这些研究主要集中在合成新的立体化学定义的“支架”，以支持催化活性的金属中心，是直接相关的药物和聚合物材料的合成，努力在其中需要立体化学控制继续增长。