Chiral Dirhodium(II) Catalysts for Carbenoid Transformations

在有机动力学项目的支持下，多伊尔博士将设计新的手性铑催化剂，用于从重氮化合物中生成类碳化合物。这些类碳化合物的分子内环化反应，例如形成内酯和内酰胺，预计会显示出异常高的对映选择性。这项工作很可能会产生重要的、新的、合成上有用的不对称合成方法。要研究的反应包括手性分子内和分子间的环丙烷化、环加成到芳香体系，以及导致内酯和内酰胺形成的碳氢插入过程。这些研究将包括：(i)催化剂制备和表征，（ii）机理研究，以及（iii）合成应用。

With support from the Organic Dynamics Program, Dr. Doyle will design new chiral rhodium catalysts that will be used to generate carbenoids from diazocompounds. Intramolecular cyclization reactions of these carbenoids that lead, e.g., to the formation of lactones and lactams are expected to display exceptionally high enantioselectivities. It is likely that significant new, synthetically useful methods for asymmetric synthesis will result from this work. The reactions to be studied include chiral intra- and inter- molecular cyclopropanations, cycloadditions to aromatic systems, and carbon-hydrogen insertion processes that result in the formation of lactones and lactams. These studies will consist of a combination of: (i) catalyst preparation and characterization, (ii) mechanistic investigations, and (iii) synthetic applications.