P,N Ligands in Asymmetric Catalysis

在有机和大分子化学项目的支持下，华盛顿大学化学系的Scott R. Gilbertson教授正在研究P， n基配体在催化不对称反应中的应用。Gilbertson教授正在开发新的膦-恶唑啉配体的合成路线，这种配体在磷上具有手性，并将磷置于[2.2.1]双环体系的桥头堡上。为了扩大含有P-C键的可接近的手性配体的范围，Gilbertson探索了乙烯基甲基酸酯催化转化为乙烯基膦，进而转化为新的配体。新配体的筛选是基于其催化一系列反应的能力，包括钯催化的pi烯丙基加成、Heck反应、不对称硼氢化和铑催化的[4+2]环异构化。许多被发现具有理想性质的有机化合物（例如，作为药物化合物）以两种形式存在，它们之间的相互关系就像右手与左手之间的相互关系一样，即互为镜像。通常情况下，一种化合物的这种同分异构体只有一种表现出理想的性质，而另一种充其量是一种无活性的污染物，最坏的情况是表现出有害的活性。选择性合成所需化合物而非其镜像的新技术的发展仍然是一个重要的研究领域。在有机和大分子化学项目的支持下，华盛顿大学化学系的Scott R. Gilbertson教授正在开发新型化合物，与各种金属离子一起，作为多种反应的催化剂，提供这种选择性。

With the support of the Organic and Macromolecular Chemistry Program, Professor Scott R. Gilbertson, of the Department of Chemistry at Washington University, is studying the synthesis of P,N-based ligands for application in catalytic asymmetric reactions. Professor Gilbertson is developing synthetic routes for new phosphine-oxazoline ligands which are chiral at phosphorus and position the phosphorus at the bridgehead of a [2.2.1] bicyclic ring system. In order to expand the range of accessible chiral ligands containing P-C bonds, Gilbertson explores the catalytic conversion of vinyl tosylates to vinylphosphines and thence to new ligands. New ligands are screened for their ability to assist in the catalysis of a mechanistically diverse range of reactions, including palladium catalyzed pi allyl addition, the Heck reaction, asymmetric hydroboration, and rhodium catalyzed [4+2] cycloisomerization.Many of the organic compounds discovered to possess desirable properties (e.g., as pharmaceutical compounds) exist in two forms, related to one another as a right hand is to a left - i.e., as mirror images. Not infrequently, only one such isomer of a compound will display the desirable properties, while the other is at best an inactive contaminant and at worst displays harmful activity. The development of new techniques for the selective synthesis of only a desired compound and not its mirror image remains a crucial area for investigation. With the support of the Organic and Macromolecular Chemistry Program, Professor Scott R. Gilbertson, of the Department of Chemistry at Washington University, is developing novel classes of compounds designed to function, together with various metal ions, as catalysts for a variety of reactions affording such selectivity.