P,N Ligands in Asymmetric Catalysis

在有机和高分子化学项目的支持下，斯科特R。华盛顿大学化学系的Gilbertson正在研究用于催化不对称反应的基于P，N的配体的合成。Gilbertson教授正在开发新的膦-恶唑啉配体的合成路线，这些配体在磷上是手性的，并且将磷定位在[2.2.1]双环系统的桥头。为了扩大含有P-C键的可获得的手性配体的范围，Gilbertson探索了乙烯基甲苯磺酸酯到乙烯基膦的催化转化，从而得到新的配体。新的配体被筛选为它们有助于催化机械上不同范围的反应的能力，包括钯催化的π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。作为药物化合物）以两种形式存在，如右手与左手一样彼此相关-即，作为镜像。通常，只有一种化合物的这种异构体会显示出所需的特性，而另一种最好是无活性的污染物，最坏的是显示出有害的活性。发展新技术，只选择性合成所需的化合物，而不是它的镜像仍然是一个重要的研究领域。在有机和高分子化学项目的支持下，斯科特R。华盛顿大学化学系的吉尔伯特森正在开发新型化合物，这些化合物被设计成与各种金属离子一起作为各种反应的催化剂，从而提供这种选择性。

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.