Asymmetric Catalysis with Ligated Copper Hydride

该项目的重点是催化的主题，特别是涉及铜（I）络合物，主要是由非外消旋双膦（（L*）CuH）连接。催化（L*）CuH对芳基酮中间体的作用将形成可用于合成已知药物的产物。催化（L*）CuH将被用于新的背景下，将提供有价值的非外消旋中间体的合成，扩展此CuH化学的限制。一个新设计的配体将被合成，以测试可能控制反应速率和对映选择性的因素。计划进行旨在研究物种（L*）CuH性质的实验，以支持提供（L*）CuH的实际来源的目标;即，实际上，CuH在瓶子里。利用硼烷作为氢化物的化学计量来源，基于金属转移反应的硼烯醇化物的合成方法将得到发展和应用。最后，木炭中的铜（Cu/C）将被探索为不对称（非均相）有机铜化学的潜在新方法。位于圣巴巴拉的加州大学化学和生物化学系的Lipshutz说。催化是开发更经济和环保技术的有力工具。Lipshutz教授和他的学生正在探索使用铜化合物催化有机化学转化的新方法。这些铜化合物比更常用的贵金属催化剂便宜得多，并且还提供独特的化学反应性。通过开发这些新的催化剂，Lipshutz教授正在开发可能普遍和广泛适用于复杂有机分子和药物合成的方法。

This project is focused on the theme of catalysis, specifically involving copper(I) hydrido complexes that are mainly ligated by nonracemic bis-phosphines ((L*)CuH). The action of catalytic (L*)CuH on aryl ketone intermediates will form products useful for the synthesis of known pharmaceuticals. Catalytic (L*)CuH will be used in new contexts that will afford valued nonracemic intermediates for synthesis, extending the limits of this CuH chemistry. A newly designed ligand will be synthesized to test the factors that may control both reaction rates and enantioselectivities. Experiments aimed at investigating the nature of the species (L*)CuH are planned, supporting the goal of providing a practical source of (L*)CuH; i.e., effectively CuH in a Bottle. Using boranes as the stoichiometric source of hydride, new inroads to boron enolates will be developed and used to synthetic advantage based on transmetalations. Finally, copper-in-charcoal (Cu/C) will be explored as a potential new approach to asymmetric (heterogeneous) organocopper chemistry.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Bruce H. Lipshutz of the Department of Chemistry and Biochemistry at the University of California at Santa Barbara. Catalysis represents a powerful tool in the development of more economical and environmentally friendly technologies. Professor Lipshutz and his students are exploring new ways to catalyze organic chemical transformations using copper compounds. These copper compounds are significantly less expensive than the more commonly used precious metal catalysts and offer unique chemical reactivity as well. By developing these new catalysts, Professor Lipshutz is developing methodologies that may be generally and broadly applicable in the synthesis of complex organic molecules and pharmaceuticals.