Exploiting Synthetic and Structural Synergism in Alkali-Metal-Mediated Organotransitionmetallation (AMMO)

利用碱金属介导的有机过渡金属化 (AMMO) 中的合成和结构协同作用

• 批准号: EP/F063733/1
• 负责人: Robert Mulvey
• 金额: $ 65.12万
• 依托单位: University of Strathclyde
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2008
• 资助国家: 英国
• 起止时间: 2008 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FF063733%2F1
• 关键词: Exploiting; Synthetic; Structural; Synergism; Alkali

The metallation reaction, where hydrogen is exchanged for a metal, is one of the most fundamental and important chemical transformations, being practised everyday in academic and industrial laboratories across the world. It is particularly useful in the manufacture of fine chemicals, pharmaceuticals, and polymers. Usually the metal employed in these reactions is lithium because of its high polarity and high reactivity. To attach a transition metal to carbon (aromatic) frameworks one would normally have to prepare the lithium derivative beforehand, then carry out a metal exchange reaction using a transition metal salt. This is necessary because transition metals are not generally reactive enough to be directly attached to an aromatic framework. However, there are limits to the usefulness of such exchange reactions due to solubility problems of the ionic salt in covalent organic solvents and to temperature sensitivities. This project will revolutionise this area as it will enable the development of the new concept of alkali-metal-mediated organotransitionmetallation (AMMO). Designing reagents containing an alkali metal and a transition metal within the same molecule, can lead to unique compounds that exhibit special synergic (mixed-metal) reactivities which cannot be replicated by alkali metal compounds or by transition metal compounds on their own (i.e. the single metal systems). Consequently using these two-metal based reagents, it is now possible to directly attach transition metal centres to aromatic frameworks. We have built prototype reagents based on lithium-manganese and sodium-manganese systems which can directly attach manganese to the carbon framework of the metallocene ferrocene, thus proving the concept. The innovative programme proposed will develop the synergic alkali metal chemistry of manganese with a range of other aromatic organic compounds and pioneer the same for other important transition metals including chromium, iron, cobalt and nickel. Incorporating transition metals with access to a large portfolio of properties (for example in redox chemistry, magnetochemistry and catalysis) within aromatic frameworks, will open up a treasure chest of new chemical opportunities outside the scope of conventional lithium-based aromatic compounds. The first transition metal host inverse crown macrocycles (special cyclic compounds with cationic host rings and anionic guest cores) will be prepared using AMMO. It is envisaged that, depending on the transition metal, some inverse crowns will exhibit interesting magnetic and material properties radically different to those of known inverse crowns which are based on magnesium and are therefore non-magnetic and non-redox active.

氢与金属的交换反应是最基本和最重要的化学转化之一，每天都在世界各地的学术和工业实验室中进行。它在精细化学品、药物和聚合物的制造中特别有用。通常，在这些反应中使用的金属是锂，因为它的高极性和高反应性。为了将过渡金属连接到碳（芳族）骨架上，通常必须预先制备锂衍生物，然后使用过渡金属盐进行金属交换反应。这是必要的，因为过渡金属通常没有足够的反应性以直接连接到芳族骨架。然而，由于离子盐在共价有机溶剂中的溶解度问题和温度敏感性，这种交换反应的有用性受到限制。该项目将彻底改变这一领域，因为它将使碱金属介导的有机过渡金属（AMMO）的新概念的发展成为可能。设计在同一分子内含有碱金属和过渡金属的试剂可以产生表现出特殊协同（混合金属）反应性的独特化合物，这些反应性不能被碱金属化合物或过渡金属化合物自身（即单金属体系）复制。因此，使用这些基于双金属的试剂，现在可以将过渡金属中心直接连接到芳族骨架上。我们已经建立了基于锂-锰和钠-锰体系的原型试剂，其可以将锰直接连接到茂金属二茂铁的碳框架上，从而证明了这一概念。拟议的创新方案将开发锰与一系列其他芳香族有机化合物的协同碱金属化学，并率先开发其他重要过渡金属，包括铬、铁、钴和镍。在芳族框架内使用具有大量特性（例如氧化还原化学，磁性化学和催化）的过渡金属，将在传统锂基芳族化合物范围之外开辟新化学机会的宝库。第一过渡金属主体反冠大环（具有阳离子主体环和阴离子客体核的特殊环状化合物）将使用AMMO制备。可以设想的是，取决于过渡金属，一些反冠将表现出与已知的基于镁的反冠完全不同的令人感兴趣的磁性和材料性质，因此是非磁性和非氧化还原活性的。

项目成果

Meta-metallation of N,N-dimethylaniline: Contrasting direct sodium-mediated zincation with indirect sodiation-dialkylzinc co-complexation.

• DOI: 10.3762/bjoc.7.144
• 发表时间: 2011
• 期刊: Beilstein journal of organic chemistry
• 影响因子: 2.7
• 作者: Armstrong DR;Balloch L;Hevia E;Kennedy AR;Mulvey RE;O'Hara CT;Robertson SD
• 通讯作者: Robertson SD

Dizincation of a 2-substituted thiophene: constructing a cage with a [16]crown-4 zincocyclic core.

• DOI: 10.1002/anie.201203344
• 发表时间: 2012-07
• 期刊: Angewandte Chemie
• 作者: Liam Balloch;Jennifer A. Garden;A. Kennedy;R. Mulvey;T. Rantanen;Stuart D. Robertson;V. Snieckus