New Methods in Organometallic and Synthetic Organic Chemistry

合成有机计划资助圣母大学化学系的Paul Helquist博士继续他在合成有机和有机金属化学中的新方法的研究。分项目之间重要的统一主题是碳环系统的构建、有机金属试剂的开发，特别是过渡金属的开发，以及不对称诱导反应的开发。首先，将研究铁-卡宾络合物，以测试这些活性中间体进行C-H插入和阳离子烯烃环化的能力。手性铁衍生物将被用来测试不对称版本的反应。第二，酮烯醇类化合物与环丙烷衍生物反应生成的中间体将被用作环戊酮环化、多环稠合环庚酮体系和三碳链段合成大环体系的前体。第三，烯烃的非对映表面选择性配位的概念以及随后配位的烯烃用于手性合成的概念将被扩展到包括一般的有机pi给体配体。

The Synthetic Organic Program is funding Dr. Paul Helquist of the Department of Chemistry at the University of Notre Dame to continue his research on new methods in synthetic organic and organometallic chemistry. The important unifying themes among the subprojects are the construction of carbocyclic ring systems, the development of organometallic reagents with a special emphasis on transition metals, and the development of reactions that take place with asymmetric induction. First, iron-carbene complexes will be studied to test the ability of these reactive intermediates to undergo C-H insertion and cationic olefinic cyclization. Chiral-at-iron derivatives will be used to test aysmmetric versions of the reactions. Second, intermediates derived from the reaction between ketone enolates and cyclopropane derivatives will be used as precursors cyclopentanone annulation, formation of polycyclic fused cycloheptanone systems and three-carbon segments for the synthesis of large-ring systems. Third, the concept of diastereofacial selective coordination of alkenes and the subsequent use of the coordinated alkenes for chiral synthesis will be extended to include organic pi-donor ligands in general.