Metal-Catalyzed Asymmetric Synthesis of Phosphorus-Carbon Bonds

David S. Glueck，达特茅斯学院化学系，因其在立体选择性P-C键形成方面的研究而受到无机、生物无机和有机金属化学项目的支持。Glueck最近发现手性Pd(0)配合物催化仲膦（RR'PH）与芳基卤化物（ArX）的不对称偶联生成手性叔膦（RR'ArP*）。探讨该反应的机理和导致高立体选择性的因素。研究的一个关键因素是钯磷络合物中磷的相对转化和还原消除速率。还将研究金属转化和还原消除的立体化学和非对映选择性。手性膦经常用于不对称催化转化，如氢化。Glueck制备的新的“手性磷”配体是对更著名的“主手性”膦的补充，其中一个手性烷基附着在磷上。除了这些潜在的工业应用之外，从事这个项目的学生将在合成、表征和催化方面发展广泛的技能。

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.