Hybrid Magnesium-Zinc Reagents:Structural Tailoring for Synthetic and Catalytic Applications

混合镁锌试剂：合成和催化应用的结构定制

• 批准号: EP/H034528/1
• 负责人: Eva Hevia
• 金额: $ 12.9万
• 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: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FH034528%2F1
• 关键词: Hybrid; Magnesium; Zinc; Reagents; Structural

Drawn up to break new ground quickly and to establish new frontiers in the area of mixed-metal chemistry, this proposal focuses on the general area of Synthesis, and specifically on the development and exploitation of a fundamental new type of organometallic reagent, namely Mg-Zn hybrids, featuring two environmentally friendly metals.One of the main missions for synthetic chemists is to improve and to add to the catalogue of reagents available, searching for new compounds that can offer enhanced reactivities but also superior selectivities and compatibility with a wide range of different substrates. In organometallic chemistry, organolithium reagents constitute one of the most important reagents in synthesis as reflected by that fact that it is estimated that 95% of the drugs manufactured in the pharmaceutical industry involve the use of these reagents at one or more steps in their synthesis. Organolithium compounds exhibit high reactivities, however their main limitation is their frequent lack of compatibility with many common organic functional groups, which ussually impose the use of sub-ambient temperatures. In this application we propose the development of an alternative type of reagent to conventional organolithium reagents, namely mixed magnesium-zinc reagents (Mg-Zn hybrids), prepared by combining two important but fundamentally distinct families of classical organometallic reagent: polar hard organomagnesium (R2Mg or RMgX) and non-polar soft organozinc (R*2Zn or R*ZnX) compounds. By using this mixed-metal approach we will instil into these compounds a new cooperative set of chemical properties and reactivity profiles, which will extend beyond the confines of traditional monometallic chemistry. A key aspect of the project will be to screen the reactivity of these new hybrids in fundamental organic reactions including metal-halogen exchange, deprotonative metallation or nucleophilic addition, not only stoichiometrically but also catalytically, by importing the high reactivity of organomagnesium reagents into organozinc reagents endowed with high functional group tolerance.

为了在混合金属化学领域迅速开辟新领域并建立新的前沿，本提案侧重于合成的一般领域，特别是开发和利用一种基本的新型有机金属试剂，即具有两种环保金属的Mg-Zn杂化物。合成化学家的主要任务之一是改进和增加可用试剂的目录，寻找新的化合物，这些化合物可以提供增强的反应性，同时也具有优越的选择性和与各种不同底物的相容性。在有机金属化学中，有机锂试剂是合成中最重要的试剂之一，据估计，制药工业生产的95%的药物在合成过程中的一个或多个步骤中都使用了这些试剂。有机锂化合物具有较高的反应活性，但其主要限制是它们经常与许多常见的有机官能团缺乏相容性，这通常迫使使用亚环境温度。在本应用中，我们建议开发一种替代传统有机锂试剂的试剂，即混合镁锌试剂（Mg-Zn杂化物），该试剂由两种重要但基本不同的经典有机金属试剂组合而成：极性硬有机镁（R2Mg或RMgX）和非极性软有机锌（R*2Zn或R*ZnX）化合物。通过使用这种混合金属方法，我们将向这些化合物注入一套新的化学性质和反应性特征，这将超越传统单金属化学的限制。该项目的一个关键方面将是通过将有机镁试剂的高反应活性引入具有高官能团耐受性的有机锌试剂中，筛选这些新杂化物在基本有机反应中的反应活性，包括金属-卤素交换、去质子金属化或亲核加成，不仅从化学计量学上而且从催化上。

项目成果

Magnesium-mediated benzothiazole activation: a room-temperature cascade of C-H deprotonation, C-C coupling, ring-opening, and nucleophilic addition reactions.

• DOI: 10.1002/anie.201103275
• 发表时间: 2011-10
• 期刊: Angewandte Chemie
• 作者: V. Blair;W. Clegg;A. Kennedy;Zoe Livingstone;Luca Russo;Eva Hevia

Alkali-metal-mediated zincation (AMMZn) meets N-heterocyclic carbene (NHC) chemistry: Zn-H exchange reactions and structural authentication of a dinuclear Au(I) complex with a NHC anion

• DOI: 10.1039/c3sc52101j
• 发表时间: 2013-01-01
• 期刊: CHEMICAL SCIENCE
• 影响因子: 8.4
• 作者: Armstrong, David R.;Baillie, Sharon E.;Hevia, Eva
• 通讯作者: Hevia, Eva

Co-complexation Syntheses, Structural Characterization, and DFT Studies of a Novel Series of Polymeric Alkali-Metal Tetraorganogallates

• DOI: 10.1021/om3009469
• 发表时间: 2013-01-28
• 期刊: ORGANOMETALLICS
• 影响因子: 2.8
• 作者: Armstrong, David R.;Brammer, Elanor;Kennedy, Alan R.
• 通讯作者: Kennedy, Alan R.

Expanding Mg-Zn hybrid chemistry: inorganic salt effects in addition reactions of organozinc reagents to trifluoroacetophenone and the implications for a synergistic lithium-magnesium-zinc activation.

• DOI: 10.1002/chem.201100866
• 发表时间: 2011-07
• 期刊: Chemistry
• 作者: D. Armstrong;W. Clegg;Pablo García‐Álvarez;A. Kennedy;Matthew D. McCall;Luca Russo;Eva Hevia