SYNTHESIS OF CHIRAL 1,2-DIAMINES VIA ASYMMETRIC ADDITION OF RLI TO 1,2-DIIMENES

这个子项目是许多研究子项目中利用 资源由NIH/NCRR资助的中心拨款提供。子项目和 调查员(PI)可能从NIH的另一个来源获得了主要资金， 并因此可以在其他清晰的条目中表示。列出的机构是 该中心不一定是调查人员的机构。 C2对称的手性1，2-二胺作为有效的催化剂配体得到了广泛的应用。它们是药物顺铂的类似物，用于癌症治疗研究。1，2-二胺也是合成天然产物的关键反应物。 传统的手性1，2-二胺合成方法是劳动密集型的，需要化学计量的手性助剂。合成手性1，2-二胺的新方法之一是在催化量的手性配体存在下，将RLI化合物加成到1，2-二亚胺上。尽管在各种不同的手性配体存在下RLI与单亚胺的加成反应已经被详尽地研究过，但到目前为止只有一篇论文描述了RLI与1，2-二亚胺的加成反应。与单亚胺反应中最成功的手性配体是双恶唑啉。目前还没有关于1，2-二亚胺在手性双恶唑存在下加成的详细研究。 本研究旨在考察在手性双恶唑啉配体存在的条件下，RLI试剂与1，2-二亚胺反应的对映体选择性。这项工作的结果将建立一种方法学，将允许直接合成手性C2对称的1，2-二胺。

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. C2-symmetric chiral 1,2-diamines with a chiral center in the ¿-position have found wide application as effective catalyst ligands. They are analogous of the drug cis-platin and are used in cancer treatment research. 1,2-Diamines are also key reactants in the synthesis of natural products. Conventional methods of chiral 1,2-diamine syntheses are labor intensive, requiring stochiometric amounts of a chiral auxiliary. One of the novel ways to synthesize chiral 1,2-diamines is by the addition of RLi compounds to 1,2-diimines in the presence of catalytic amounts of a chiral ligand. Despite the fact that addition of RLi to monoimines in the presence of a variety of different chiral ligands has been exhaustively studied, only one paper has been published to date describing the addition of RLi to 1,2-diimines. The most successful chiral ligands used in reactions with monoimines are bis-oxazolines. No research detailing addition to 1,2-diimines in the presence of chiral bis-oxazolines has been published. The proposed research is to investigate the enantioselectivity of the addition of RLi reagents to 1,2-diimines in the presence of stochiometric and substochiometric amounts of chiral bis-oxazoline based ligands. The results of this work should establish a methodology that will allow a straight-forward synthesis of chiral C2-symmetric 1,2-diamines.