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

多官能团金属有机化合物是有机合成的重要组成部分。在这个项目中，我们将开发一种新的制备多官能团锌金属有机化合物的方法，使用一种新的In(III)催化的锌插入芳基和杂芳基溴化物和碘化物。我们将研究一种新的在碳氢化合物中用卤素/镁交换法制备二芳基和二杂芳基镁试剂R2 Mg-2ROLi。我们还将通过卤素或亚硫氧化物交换La来制备多官能团La-金属化合物，并研究它们对羰基和其他亲电性的反应性。我们将制备新的固体锌Reformzki试剂，并将这些试剂用于多肽的后期功能化。我们还将研究钴和铬催化的新的交叉偶联反应，我们的主要目标是找到允许锌或镁有机金属化合物和有机卤化物之间普遍发生CSP2-CSP2交叉偶联的反应条件。还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，这一研究项目应该会产生具有学术和工业应用的有用的合成方法。

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.