Highly Enantioselective Copper(I) and Dirhodium(II) Catalysts

通过这项更新提案，有机和高分子化学计划支持亚利桑那大学的Michael P. Doyle博士的工作。 这项工作建立在早期的结果，使用不对称金属卡宾转换分子内环丙烷化和C-H插入使用手性dirhodium（II）carboxamidate配合物合成有机化合物难以通过其他手段。 他计划通过修饰甲酰胺配体来提高二铑催化剂的反应性，研究双重非对映选择，进行不对称叶立德转化，产生环原子数高达20个的大环化合物，并确定了配体的空间和电子因素在决定催化剂产率和选择性方面的重要性。这项工作涉及基础研究，改进了利用手性有机化合物合成手性有机化合物的方法，具有手性配体的均相催化剂。 这些方法可能在药物和农业化学品的合成中是有用的。 在过去的五年里，Doyle博士帮助培训了23名本科生，他们在Doyle博士的实验室与博士后学生一起工作。

With this renewal proposal the Organic and Macromolecular Chemistry Program supports the work of Dr. Michael P. Doyle at the University of Arizona. The work builds on earlier results using asymmetric metal carbene transformations for intramolecular cyclopropanation and C-H insertion using chiral dirhodium(II) carboxamidate complexes to synthesize organic compounds difficult to make by other means. He plans to increase the reactivity of the dirhodium catalysts by modifying the carboxamidate ligands, investigate double diastereoselection, carry out asymmetric ylide transformations, produce macrocyclic compounds with rings of up to 20 atoms, and determine the importance of ligand steric and electronic factors in determining catalyst yields and selectivities.This work involves fundamental research in improved ways to synthesize chiral organic compounds using homogeneous catalysts with chiral ligands. The methods are likely to be useful in the synthesis of pharmaceuticals and agricultural chemicals. Dr. Doyle has helped to train 23 undergraduate students in the past five years, in a unique arrangement in which they work with postdoctoral students in Dr. Doyle's laboratory.