Organoiron Complexes in Organic Synthesis

本项目将继续研究在首席研究员实验室发现的涉及有机铁络合物的新反应的开发和应用。 具体而言，将研究与三羰基铁络合的二烯与烯烃之间的环偶联反应的范围，即[6+2]烯的缩甲醛反应。 这种反应类型是三羰基铁络合物所独有的，并且需要化学计量使用有机金属基团以防止竞争性分子内Diels-Alder反应。 该烯反应的不对称双版本的应用，以串联的方式进行，将探索作为一种方法的化学合成的18-脱氧细胞松弛素H，这是作为一种HIV蛋白酶抑制剂的兴趣。 还将研究这种[6+2]烯反应的变体，其中侧链烯烃被醛和亚胺官能团取代，这拓宽了该方法的范围。 将串联烯烃/醛[6+2]烯反应应用于化学合成Magellaninone，一种结构复杂的石松生物碱天然产物，将作为一个长期的未来目标。有了这个奖项，有机和大分子化学计划将支持凯斯西储大学化学系的Anthony J. Pearson教授的研究。 皮尔逊教授的研究工作围绕着金属介导的C-C键形成反应的发展。 这种化学反应将有助于环境友好的化学合成方法，因为容易获得的铁被用作介导关键反应的活性金属。 该方法的成功开发将对制药和农业工业的合成产生影响。

This project will continue research on the development and applications of new reactions involving organoiron complexes discovered in the Principal Investigator's laboratory. Specifically, the scope of cyclocoupling reactions between a diene complexed with an iron tricarbonyl group and an alkene, the formal [6+2] ene reactions, will be studied. This reaction type is unique to iron tricarbonyl complexes and requires the stoichiometric use of the organometallic group to prevent competing intramolecular Diels-Alder reactions. The application of an asymmetric double version of this ene reaction, carried out in a tandem manner, will be explored as an approach to the chemical synthesis of 18-deoxycytochalasin H, which is of interest as an HIV protease inhibitor. A variant of this [6+2] ene reaction in which the pendant alkene is replaced by aldehyde and imine functionality, which broadens the scope of the process, will also be studied. Application of tandem alkene/aldehyde [6+2] ene reactions to the chemical synthesis of magellaninone, a structurally complex lycopodium alkaloid natural product, will be pursued as a long term future goal.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Anthony J. Pearson of the Department of Chemistry at Case Western Reserve University. Professor Pearson's research efforts revolve around the development of metal-mediated reactions for the formation of C-C bonds. Such chemistry will contribute to environmentally benign methods for chemical synthesis as the readily available iron is used as the active metal that mediates the key reactions. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.