Structure and Reactivity of Mixed Aggregates of Lithium Alkyls and Alkoxides

北卡罗来纳大学夏洛特分校的克雷格·奥格尔的这个项目是有机动力学项目的一部分，旨在更好地了解有机锂化合物。有机硫是合成多种有机化合物的重要中间体，这项研究将通过一种相对较新的技术--快速注入核磁共振光谱来阐明它们的结构。烷基锂试剂的反应性通常通过添加醇盐来改变。混合碱在金属化、聚合和烷基化反应中被广泛使用，但对试剂是如何改变的没有清楚的了解。本研究的目的是为了从根本上理解烷基锂和混合聚集体与亲电试剂的反应机理，这可能会导致更多活性和选择性试剂的开发。这项工作将包括制备和鉴定IA和IIA组的有机锂硫化物和烷氧化合物的混合聚集体。然后用Li-7和H-1快速注入核磁共振研究这些混合聚集体对亲电性和碳酸的反应性。还将研究烷基锂与亲电试剂反应形成的混合聚集体。

This project by Craig Ogle of the University of North Carolina, Charlotte is within the Organic Dynamics Program, and is aimed at a better understanding of organolithium compounds. Organolithiums are important intermediates in the synthesis of a wide variety of organic compounds, and this research will provide the elucidation of their structure by a relatively new technique known as rapid injection nuclear magnetic resonance spectroscopy. The reactivity of alkyllithium reagents is often modified by the addition of alkoxides. Mixed bases have been used extensively in metalations, polymerizations and alkylations, without a clear understanding of how the reagent is being changed. This study is aimed at providing a fundamental understanding of the mechanism of the reaction of alkyllithiums and mixed aggregates with electrophiles; this may lead to the development of more reactive and selective reagents. The work will consist of the preparation and identification of mixed aggregates of organolithiums and alkoxides of groups IA and IIA. The reactivity of these mixed aggregates towards electrophiles and carbon acids will then be investigated by Li-7 and H-1 rapid injection NMR. Mixed aggregates formed from the reaction of alkyllithiums with electrophiles will also be investigated.