P,N Ligands in Asymmetric Catalysis

在有机化学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基配体的合成，用于催化不对称反应。Gilbertson教授正在开发新的膦-恶唑啉配体的合成路线，这些配体在磷原子上是手性的，并将磷定位在[2.2.1]双环体系的桥头。为了扩大含有P-C键的手性配体的范围，Gilbertson探索了乙烯基对甲苯磺酸盐催化转化为乙烯基膦，然后再转化为新的配体。新的配体被筛选为它们能够帮助催化一系列机械上不同的反应，包括钯催化的pi-烯丙基加成，Heck反应，不对称氢化硼化，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，彼此之间的关系就像右手和左手的关系-即镜像。通常，一种化合物只有一个这样的异构体会显示出理想的性质，而另一个充其量是一种不活跃的污染物，而在最坏的情况下显示出有害的活性。开发只选择性合成所需化合物而不是其镜像的新技术仍然是一个关键的研究领域。在有机化学和高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，这些化合物与各种金属离子一起用作催化剂，用于各种具有这种选择性的反应。

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.