Synthetic and Mechanistic Studies of Palladium-Catalyzed Asymmetric Phosphination

达特茅斯学院化学系的David Glueck在无机化学、生物无机化学和金属有机化学计划的支持下，开发了制备光学活性膦的催化方法。P-立体构型手性配体的形成将是对目前可用于催化剂制备的C-中心手性配体的重要补充。本课程将研究膦及其硼烷加合物中P-C键的催化形成。Pd催化的不对称磷酸化反应中的对映体选择处于Curtin-Hammett控制下的假设将得到验证。手性配体在不对称催化中起着至关重要的作用。这个项目将产生机制信息，这些信息将指导设计新的路线，以获得磷原子上的手性磷配体。利用手性磷配体开发更有效和更具选择性的不对称催化剂的潜力将被探索。

David Glueck, Department of Chemistry, Dartmouth College, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program to develop catalytic methods to prepare optically active phosphines. The formation of P-stereogenic chiral ligands will be an important addition to the repertoire of C-centered chiral ligands currently available for catalyst preparation. Catalytic formation of P-C bonds in phosphines and their borane adducts will be investigated. The hypothesis that enantioselection in Pd-catalyzed asymmetric phosphination is under Curtin-Hammett control will be tested. Chiral ligands are essential to asymmetric catalysis. This project will generate mechanistic information that will guide the design of new routes to phosphorus ligands that are chiral at the phosphorus atom. The potential for developing more efficient and more selective asymmetric catalysts using chiral-at-phosphorus ligands will be explored.