Metal-Catalyzed Asymmetric Synthesis of Phosphorus-Carbon Bonds

达特茅斯学院化学系的David S.Glueck因其在立体选择性P-C键形成方面的工作而得到了无机、生物无机和有机金属化学计划的支持。Glueck最近发现，手性Pd(0)络合物催化仲膦(RR‘PH)与芳基卤化物(ARX)的不对称偶联，得到手性叔膦(RR’Arp*)。探讨了该反应的反应机理和导致高立体选择性的因素。需要研究的一个关键因素是钯磷络合物中磷转化和还原消除的相对速度。手性膦经常用于不对称催化转化，如氢化反应。Glueck制备的新的“手性磷”配体是对更著名的“主链手性”膦的补充，其中手性烷基连接到磷上。除了这些潜在的工业应用外，从事该项目的学生还将发展合成、表征和催化方面的广泛技能。

David S. Glueck, Department of Chemistry, Dartmouth College, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for his work on stereoselective P-C bond formation. Glueck has recently shown that a chiral Pd(0) complex catalyzes the asymmetric coupling of a secondary phosphine (RR'PH) with an aryl halide (ArX) to give a chiral tertiary phosphine (RR'ArP*). The mechanism of this reaction and the factors leading to the high stereoselectivity will be explored. One key factor to be studied is the relative rate of phosphorus inversion and reductive elimination in Pd phosphido complexes. The stereochemistry and diastereoselectivity of transmetalation and of reductive elimination will also be examined.Chiral phosphines are frequently used in asymmetric catalytic transformations such as hydrogenation. The new "chiral at phosphorus" ligands prepared by Glueck are a complement to the better-known "backbone chirality" phosphines where a chiral alkyl group is attached to the phosphorus. In addition to these potential industrial applications, students working on this project will develop a broad set of skills in synthesis, characterization and catalysis.