Lithium Cuprates to Copper Lithiates: A New Dawn in Metal Catalysed Chemistry

至少在过去的一万年里，人类一直在使用铜金属。“天然铜”是最早发现的金属之一，因为它可以以不结合的形式存在，而不像大多数其他活性金属那样是天然矿物。在20世纪，铜成为电线、管道、建筑和工业机械的重要金属，主要是由于其良好的化学和物理性能，包括其延展性、非常高的导电性和导热性、耐久性和耐腐蚀性。铜还具有重要的生物学作用。它是一种必需的微量元素，对人体器官和新陈代谢的正常运作至关重要。铜通常被认为是一种非常不活泼的金属；然而，当它与有机（含碳）分子化学结合产生有机铜化合物时，情况就大不相同了。甲基铜是最早合成的有机铜试剂之一，它实际上具有高度爆炸性，而且反应性太强，无法产生安全、可控和可重复的化学反应。但是，当与有机锂化合物结合时，新的混合锂铜试剂显示出更高的稳定性，可以产生令人兴奋的，有用的化学反应，允许开发多种催化化学转化。这使得新的重要分子的简单合成成为可能，在过去的几年里，这些分子已经改变了制药业。到目前为止，基础科学研究表明，这些锂铜试剂以“铜酸锂”的形式存在，这意味着锂中心带正电，而铜中心带负电的有机基团使其带负电。在我们的团队中，我们最近取得了突破，有可能制备出一种全新的锂铜化合物，其中每种金属的正负作用被逆转，产生了前所未有的锂铜酸盐。在本项目中，将充分探索具有这种新配方和极性反转的化合物的形成范围和催化反应性。这一混合锂铜化学“新方向”的结果无疑将吸引广泛的学术界，包括无机、有机金属和有机化学家，以及由于前所未有的结构和配位化学而吸引超分子化学家。这种扩展到催化的新方法也将引起化学工业（精细化学品、制药、农用化学品等）研究人员的极大兴趣，他们努力以一种简便的方式生产新的关键分子，以造福人类。

Copper metal has been used by humans for at least the past 10,000 years. "Native copper" was one of the first metals discovered as it can exist in an uncombined form, and not as a natural mineral like most other more reactive metals. In the 20th century, copper emerged as an important metal for electrical wiring, pipework, architecture and industrial machinery, mainly due to its favourable chemical and physical properties including its ductility, very high electrical and thermal conductivity, durability and corrosion resistance. Copper also has an important biological role. It is an essential trace element, which is vital for the proper functioning of the body's organs and metabolism.Copper is generally considered as a very unreactive metal; however, when it is chemically-combined with an organic (carbon-containing) molecule to produce an organocopper compound, a vastly different situation arises. One of the first organocopper reagents synthesised, methylcopper, is in fact highly explosive and too reactive to produce a safe, manageable and reproducible chemistry. But when combined with an organolithium compound, the new mixed lithium copper reagent displays a much higher stability which can be harvested to produce an exciting, useful chemistry allowing for a multitude of catalytic chemical transformations to be developed. This has allowed the facile synthesis of new important molecules, which over the past few years have transformed the pharmaceutical industry. Up until now, the fundamental science at play has dictated than these lithium copper reagents exist as "lithium cuprates" meaning that the lithium centre is formally positively charged, whilst the copper centre holds the negatively charged organic groups rendering it formally negatively charged. In our group, we have recently made the breakthrough that it is possible to prepare a brand new type of lithium copper compound, where the positive-negative role that each metal plays has been reversed, producing an unprecedented copper lithiate. In this project, the scope of formation and catalytic reactivity of compounds displaying this new formulation and polarity reversal will be fully explored. Results from this "new direction" within mixed lithium copper chemistry will undoubtedly appeal to a broad spectrum of academics, including inorganic, organometallic and organic chemists, as well as to supramolecular chemists due to the unprecedented structural and coordination chemistry. This new methodology extended to catalysis will also be of considerable interest to researchers in the chemical industry (fine chemicals, pharmaceutical, agrochemical etc.) who strive to produce new key molecules in a facile manner for the benefit of humankind.