Lithium Cuprates to Copper Lithiates: A New Dawn in Metal Catalysed Chemistry
Lead Research Organisation:
University of Strathclyde
Department Name: Pure and Applied Chemistry
Abstract
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.
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.
Planned Impact
Variety of academics including those in coordination, inorganic, organometallic, organic and materials chemistry fields
Industrial chemists who utilise stoichiometric and catalytic organometallic chemistry, i.e. those involved in pharmaceuticals, perfumery, agrochemicals and fine chemicals industries
Ultimately, general public when new technology is implemented by the aforementioned industries
Full details are provided in the Pathways to Impact document.
Industrial chemists who utilise stoichiometric and catalytic organometallic chemistry, i.e. those involved in pharmaceuticals, perfumery, agrochemicals and fine chemicals industries
Ultimately, general public when new technology is implemented by the aforementioned industries
Full details are provided in the Pathways to Impact document.
Organisations
People |
ORCID iD |
Charles O'Hara (Principal Investigator) |
Publications
Armstrong DR
(2013)
Evaluating cis-2,6-dimethylpiperidide (cis-DMP) as a base component in lithium-mediated zincation chemistry.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Clegg W
(2013)
Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone.
in Dalton transactions (Cambridge, England : 2003)
Francos J
(2014)
Optimisation of a lithium magnesiate for use in the non-cryogenic asymmetric deprotonation of prochiral ketones.
in Dalton transactions (Cambridge, England : 2003)
Francos J
(2014)
Complexity in seemingly simple sodium magnesiate systems.
in Dalton transactions (Cambridge, England : 2003)
Francos J
(2015)
Structural Studies of ( rac )-BIPHEN Organomagnesiates and Intermediates in the Halogen-Metal Exchange of 2-Bromopyridine
in Organometallics
Francos J
(2016)
Synthetic and reactivity studies of hetero-tri-anionic sodium zincates.
in Dalton transactions (Cambridge, England : 2003)
Fuentes MÁ
(2016)
Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Kennedy A
(2014)
Synthesis of an alkylmagnesium amide and interception of a ring-opened isomer of the important utility amide 2,2,6,6-tetramethylpiperidide (TMP)
in Inorganica Chimica Acta
Kennedy AR
(2014)
Dehydromethylation of alkali metal salts of the utility amide 2,2,6,6-tetramethylpiperidide (TMP).
in Chemical communications (Cambridge, England)
Martínez-Martínez A
(2014)
Pre-inverse-crowns: synthetic, structural and reactivity studies of alkali metal magnesiates primed for inverse crown formation
in Chem. Sci.
Title | Selective Mono-and Dimetallation of a Scandium Cp/COT hybrid Sandwich Complex by Lithium-Aluminium Trans-Metal Trapping |
Description | Word documents containing: (1) general experimental procedures; (2) NMR spectra; (3) X-ray crystallographic data; and (4) DFT computational data. |
Type Of Art | Film/Video/Animation |
Year Produced | 2019 |
URL | https://pureportal.strath.ac.uk/en/datasets/f3d8e22f-5565-43a3-97fb-b3e09b628cd0 |
Description | The major breakthrough in this project was the synthesis, characterisation and utility of a series of template metal bimetallic bases. The unique shape of these bases allows them to react with common and crucially important aromatic molecules in hitherto inaccessible positions, results which will potentially have a high impact on making new or existing (in an easier manner) pharmaceuticals. The results from these studies were reported in Chemical Science and Science. |
Exploitation Route | A major finding from our studies was that the template bases used in this project can be made without the use of glove boxes. This opens up the chemistry to virtually any organic synthetic laboratory in the world. In addition, solutions of the bases are stable for months, again increasing the user-friendliness of the reagents. |
Sectors | Chemicals |
Title | Exploring the Solid State and Solution Structural Chemistry of the Utility Amide Potassium Hexamethyldisilazide (KHMDS) |
Description | Word doc containing X-ray data and NMR data |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Impact | Unknown |
Title | Monodentate coordination of the normally chelating chiral diamine (R,R)-TMCDA |
Description | The data set contains a MS word document containing X-ray and NMR data as well as synthetic protocols. In addition X-ray files are included |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Impact | n/a |
Title | Structural studies of cesium, lithium/cesium and sodium/cesium bis(trimethylsilyl)amide (HMDS) complexes |
Description | The data set contains two MS word documents containing supplementary information (one for X-ray crystallographic data, the other NMR spectroscopic data) and supports the related research publication. In the paper a new method for preparing CsHMDS is reported. In addition, the structures and syntheses of two polymeric mixed alkali metal HMDS complexes are detailed. Finally, the structural chemistry (solid- and solution-state) of CsHMDS with different multidentate donors is described. |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Impact | n/a |
Title | Templated Deprotonative Metalation of Polyaryl Systems: Facile Access to Simple, Previously Inaccessible Multi-iodoarenes |
Description | MS Word document containing supplementary information on X-ray and NMR (Nuclear Magnetic Resonance) data for all compounds in the related paper. Data embargo until 24/11/17 |
Type Of Material | Database/Collection of data |
Provided To Others? | No |
Impact | n/a |