Asymmetric Catalysis with Ligated Copper Hydride

本项目以催化为主题，特别涉及铜(I)氢氧配合物，主要由非外消旋双膦（(L*)CuH）连接。催化（L*）CuH对芳基酮中间体的作用将形成对合成已知药物有用的产物。催化（L*）CuH将在新的环境中使用，将为合成提供有价值的非外消旋中间体，扩展这种CuH化学的极限。将合成一种新设计的配体来测试可能控制反应速率和对映体选择性的因素。计划进行旨在调查（L*）CuH物种性质的实验，以支持提供（L*）CuH的实际来源的目标；也就是说，有效的瓶中CuH。以硼烷为氢化物的化学计量源，开发硼烯醇化物的新途径，并将其用于基于金属转化的合成优势。最后，将探讨炭中铜（Cu/C）作为不对称（非均相）有机铜化学的潜在新途径。通过这个奖项，有机和大分子化学项目支持加州大学圣巴巴拉分校化学和生物化学系的Bruce H. Lipshutz博士的研究。催化是开发更经济、更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，而且具有独特的化学反应活性。通过开发这些新的催化剂，Lipshutz教授正在开发一种可以广泛应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.