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

通过 RLI 不对称加成到 1,2-二亚胺合成手性 1,2-二胺

• 批准号: 8360426
• 负责人: NATALIA F BLANK
• 金额: $ 6.34万
• 依托单位: UNIVERSITY OF VERMONT & ST AGRIC COLLEGE
• 依托单位国家: 美国
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-06-01 至 2012-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8360426
• 关键词: Biological Factors; Diamines; Funding; Genetic; Grant; Ligands; Methodology; Methods; National Center for Research Resources; Paper; Pharmaceutical Preparations; Positioning Attribute; Principal Investigator; Publishing; Reaction; Reagent; Research; Research Infrastructure; Resources; Source; United States National Institutes of Health; Vermont; Work; base; cancer therapy; catalyst; cost; novel

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.

这个子项目是利用资源的许多研究子项目之一。 由NIH/NCRR资助的中心拨款提供。对子项目的主要支持 子项目的首席调查员可能是由其他来源提供的， 包括美国国立卫生研究院的其他来源。为子项目列出的总成本可能 表示该子项目使用的中心基础设施的估计数量， 不是由NCRR赠款提供给次级项目或次级项目工作人员的直接资金。 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。