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

这个子项目是许多利用资源的研究子项目之一 由NIH/NCRR资助的中心拨款提供。子项目的主要支持 而子项目的主要调查员可能是由其他来源提供的， 包括其它NIH来源。 列出的子项目总成本可能 代表子项目使用的中心基础设施的估计数量， 而不是由NCRR赠款提供给子项目或子项目工作人员的直接资金。 手性中心在<$-位的C2-对称手性1，2-二胺作为有效的催化剂配体有着广泛的应用。它们类似于药物顺铂，用于癌症治疗研究。1，2-二胺也是天然产物合成中的关键反应物。 手性1，2-二胺合成的常规方法是劳动密集型的，需要化学计量量的手性助剂。合成手性1，2-二胺的新方法之一是通过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与单亚胺的加成已经被详尽地研究，但迄今为止仅发表了一篇描述RLi与1，2-二亚胺加成的论文。在与单亚胺的反应中使用的最成功的手性配体是双恶唑啉。没有研究详细说明在手性双恶唑啉存在下加成到1，2-二亚胺。 本论文主要研究了在化学计量和亚化学计量的手性双恶唑啉配体存在下，RLi试剂与1，2-二亚胺加成反应的对映选择性。这项工作的结果应该建立一种方法，将允许一个直接的手性C2-对称的1，2-二胺的合成。

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. Primary support for the subproject and the subproject's principal investigator may have been provided by other sources, including other NIH sources. The Total Cost listed for the subproject likely represents the estimated amount of Center infrastructure utilized by the subproject, not direct funding provided by the NCRR grant to the subproject or subproject staff. 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.