New Synthetic Applications of Eco-friendly Organometallics of Magnesium, Zinc and Lanthanum in Organic Synthesis

镁、锌、镧环保有机金属化合物在有机合成中的合成新应用

• 批准号: 331331543
• 负责人: Professor Dr. Paul Knochel
• 金额: --
• 依托单位: Department Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/331331543?language=en
• 关键词: New; Synthetic; Applications; Eco; friendly

Polyfunctional organometallics are important building blocks for organic synthesis. In this project, we will develop a new preparation method of polyfunctional Zn-organometallics using a new In(III)-catalyzed zinc insertion to aryl and heteroaryl bromides and iodides. We will study a new preparation of diaryl- and diheteroaryl-magnesium reagents of the type R2Mg-2ROLi in hydrocarbons using a halogen/magnesium-exchange. We will also prepare polyfunctional La-organometallics via a halogen- or sulfoxide-lanthanum-exchange and study their reactivity toward carbonyl groups and other electrophiles. We will prepare new solid zinc Reformatzki-reagents and use these reagents to perform late-stage functionalization of peptides. We will also investigate new Co- and Cr-catalyzed cross-couplings and our main aim is to find reaction conditions allowing a general Csp2-Csp2 cross-coupling between zinc or magnesium organometallics and organic halides. Diastereoselective cross-couplings will also be studied as well as new electrophilic amination reactions. All projects are supported by preliminary experiments and useful synthetic methodologies with academic and industrial applications should result from this research project.

多功能金属有机化合物是有机合成的重要组成部分。在本计画中，我们将发展一种新的多官能锌金属有机化合物的制备方法，使用一种新的铟（III）催化的锌插入到芳基和杂芳基的溴化物和碘化物中。我们将研究一种新的制备二芳基和二杂芳基镁试剂的类型R2 Mg-2 ROLi在烃中使用卤素/镁交换。我们还将通过卤素或亚砜镧交换制备多官能La-有机金属化合物，并研究它们对羰基和其他亲电体的反应性。我们将制备新的固体锌Reformatzki试剂，并使用这些试剂进行肽的后期功能化。我们还将研究新的Co和Cr催化的交叉偶联，我们的主要目的是找到允许锌或镁有机金属化合物和有机卤化物之间的一般Csp 2-Csp 2交叉偶联的反应条件。也将研究非对映选择性交叉偶联以及新的亲电胺化反应。所有项目都得到了初步实验的支持，并且具有学术和工业应用的有用合成方法应该来自该研究项目。