Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry

极性有机金属化学原理和实践的范式转变

• 批准号: EP/N011384/1
• 负责人: Eva Hevia
• 金额: $ 48.36万
• 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: 2015
• 资助国家: 英国
• 起止时间: 2015 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FN011384%2F1
• 关键词: Towards; Paradigm; Shift; Principles; Practice

Polar organometallic chemistry provides an essential toolkit for transforming inert bonds into reactive bonds to make new compounds and materials. Very few aromatic molecules (e.g., pharmaceuticals, agrochemicals, perfumes) are made without polar organometallic chemistry being practiced at some stage in their manufacture. Though this chemistry has a long and successful history, it is currently at an exciting crossroads in its development with seemingly impossible challenges within it now on the verge of becoming possible. This project is designed towards fundamentally reforming the practice of polar organometallic chemistry making it more air and moisture compatible, greener, more atom-economical and sustainable. Research will focus on the synthesis, cultivation and exploitation of new s-block metal multicomponent reagents made by co-complexation protocols. Preliminary work has shown that mixing different components within the same environment (for example, two distinct metal complexes; or one metal but with an assortment of ligands) can lead to useful synergistic effects not possible with unmixed systems. The scope of the chemistry and the ability to construct new compounds and new materials to meet societal needs are thus greatly broadened. Based on earth-abundant metals, these co-complex reagents will be screened in key organic transformations, focusing on deprotonative metallation and metal-halogen exchange reactions as well as in tandem C-C bond forming methods (as an alternative to more expensive and less environmentally benign transition-metal-mediated approaches) targeting synthetically relevant organic substrates. Stoichiometric reactions will be upgraded to catalytic regimes to establish the ground rules for s-block synergistic catalysis focusing on intramolecular hydroamination reactions of a range of unsaturated molecules. A key objective of the project is to pioneer and extend the use of multicomponent polar organometallic reagents in Deep Eutectic Solvents (DESs). These DESs will provide more cost-effective, greener and biorenewable reaction media to those volatile organic solvents (VOC's) in which most polar organometallic chemistry is carried out today. Progress in this aim will go a long way to eventually realising the "impossible" challenge in polar organometallic chemistry of synthesising and utilising chemoselective organometallic reagents under air and/or in aqueous media. Dispensing with the need for a dry inert atmosphere would have genuine worldwide implications for the practice of polar organometallic chemistry both in academia and industry.

极性金属有机化学为将惰性键转化为反应键以制备新化合物和材料提供了重要的工具包。很少有芳香族分子(例如，药品、农用化学品、香水)的制造过程中没有在其制造的某个阶段进行极性金属有机化学的练习。尽管这种化学有着悠久而成功的历史，但它目前正处于其发展的令人兴奋的十字路口，其内部看似不可能的挑战现在即将成为可能。该项目旨在从根本上改革极性有机金属化学的实践，使其更适合空气和水分，更环保，更节约原子和可持续发展。研究将集中在共络合法制备新型S嵌段金属多元试剂的合成、培育和开发。初步工作表明，在同一环境中混合不同的组分(例如，两个不同的金属络合物；或一个金属但带有各种配体)可以产生有用的协同效应，而不混合的体系是不可能的。因此，化学的范围和构建新化合物和新材料以满足社会需求的能力大大拓宽了。基于地球上丰富的金属，这些配位试剂将在关键的有机转化中进行筛选，重点是去质子化金属和金属-卤素交换反应，以及针对合成相关有机底物的串联C-C键形成方法(作为更昂贵和环境友好的过渡金属介导法的替代方法)。化学计量反应将升级为催化体系，以建立S-嵌段协同催化的基本规则，重点关注一系列不饱和分子的分子内氢胺化反应。该项目的一个关键目标是开拓和推广多组分极性金属有机试剂在深度共熔溶剂(DESS)中的使用。这些DESS将为挥发性有机溶剂(VOC)提供更具成本效益、更环保和可生物可再生的反应介质，目前大多数极性有机金属化学都是在VOC中进行的。这一目标的进展将大大有助于最终实现在极性有机金属化学中在空气和/或水介质中合成和利用化学选择性有机金属试剂这一“不可能的”挑战。消除对干燥的惰性气氛的需要将对学术和工业中的极性有机金属化学的实践产生真正的世界性影响。

项目成果

LiTMP Trans-Metal-Trapping of Fluorinated Aromatic Molecules: A Comparative Study of Aluminum and Gallium Carbanion Traps.

LITMP氟化芳香族分子的跨金属陷阱：铝和甘油carbanion陷阱的比较研究。

• DOI: 10.1002/anie.201706064
• 发表时间: 2017-08-01
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: McLellan R;Uzelac M;Kennedy AR;Hevia E;Mulvey RE
• 通讯作者: Mulvey RE

LiTMP Trans-Metal-Trapping of Fluorinated Aromatic Molecules: A Comparative Study of Aluminum and Gallium Carbanion Traps

LiTMP 跨金属捕获氟化芳香族分子：铝和镓碳负离子陷阱的比较研究

• DOI: 10.1002/ange.201706064
• 发表时间: 2017
• 期刊: Angewandte Chemie
• 作者: McLellan R

Exploiting Deprotonative Co-complexation to Access Potassium Metal(ates) Supported by a Bulky Silyl(bis)amide Ligand

• DOI: 10.1002/ejic.202001051
• 发表时间: 2021-01-20
• 期刊: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
• 影响因子: 2.3
• 作者: Mastropierro, Pasquale;Kennedy, Alan R.;Hevia, Eva
• 通讯作者: Hevia, Eva

Structurally Mapping Alkyl and Amide Basicity in Zincate Chemistry: Diversity in the Synthesis of Mixed Sodium-Zinc Complexes and Their Applications in Enolate Formation

• DOI: 10.1021/acs.organomet.0c00339
• 发表时间: 2020-12-14
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Mastropierro, Pasquale;Livingstone, Zoe;Hevia, Eva
• 通讯作者: Hevia, Eva