Synthesis and Reactivity of Substituted Cyclopentadienylmetals

提出的研究在环戊二烯金属配合物的背景下解决了几个主要目标。将开发有效的合成方法来合成已知的环戊二烯基配体和配合物以及新的手性环戊二烯基和独立基金属配合物。将合成手性独立基和环戊二烯基配体，并与金属配位。最后，探讨手性配合物在对映选择性碳-碳和碳氢键形成反应中的活性。配体的合成将通过利用2-溴茚基配合物的交叉偶联反应、合环复分解反应（苯基二烯生成茚）和铬(II)/镍羰基加成法将溴芳烃或溴烯与酮或醛转化为取代茚和环戊二烯来实现。有了这个奖项，有机合成项目支持了俄克拉何马大学化学和生物化学系的Ronald L. Halterman教授的研究。Halterman教授的研究方向是合成新的催化剂，旨在通过精确控制产物的详细三维结构（“立体化学”）来影响碳-碳和碳氢键的形成。这些研究主要集中在合成新的立体化学定义的“支架”来支持催化活性金属中心，与药物和聚合物材料的合成直接相关，在这些研究中，对立体化学控制的需求不断增长。

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.