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

有了这项更新提案，有机和高分子化学项目支持了亚利桑那大学迈克尔·P·道尔博士的工作。这项工作建立在早期的结果基础上，使用不对称金属卡宾转化进行分子内环丙化和C-H插入，使用手性二氢呋喃(II)碳酰胺配合物合成其他方法难以制备的有机化合物。他计划通过修饰羧氨酸酯配体来提高镝催化剂的反应活性，研究双非对映选择，进行不对称叶立德转化，产生最多20个原子的环的大环化合物，并确定配体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。这项工作涉及改进方法的基础研究，使用带有手性配体的均相催化剂合成手性有机化合物。这些方法很可能在药物和农用化学品的合成中有用。在过去的五年里，多伊尔博士帮助培训了23名本科生，他们在多伊尔博士的实验室与博士后一起工作，这是一种独特的安排。

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.