Improved Liquid and Mixed Metal Activation for Organic Synthesis
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Chemistry
Abstract
This present application represents a revised immediate resubmission of EP/G00272X/1 (considered early June 2008) it was highly rated but insufficient funds were available to the prioritisation panel. Referee comments on the lead science in this application were very strong (e.g. 'most novel and refreshing proposal I haves seen', 'truly excellent ideas', 'outstanding', etc.) but the funding environment did not allow its support.We have found that catalytic liquid gallium can be used for highly efficient unprecedented metal activation allowing simplified rapid preparation of organometallics RM and metal hydrides. The technique allows formation of new unprecedented air-stable aryl alanes; direct use metal-mixtures for improved/efficient RX and hydrogen and amine activation to provide Al-hydrides [HAl(NR2)2] and [HAl(NR2)Cl] and the DABCO stabilized air-stable organometallics [(RnY3-n)2(DABCO)] (Y = I, NR2). These derived reagents are to be used in fast throughput (asymmetric) screening of 1,2-additions to FG-RCHO and imines; 1,4-additions to unsaturated acylcyanides; alkene and alkyne hydroalumination and their subsequent use in related processes.
People |
ORCID iD |
S Woodward (Principal Investigator) |
Publications
Asikainen M
(2010)
An SN2' displacement approach to allenyl acetates
in Tetrahedron Letters
Conte V
(2010)
Palladium-catalysed methylation of aryl halides in ionic liquids with stabilized AlMe3
in Applied Catalysis A: General
Crampton R
(2011)
Bis-Sulfamyl Imines: Potent Substrates for Asymmetric Additions of Arylboroxines under Rhodium Catalysis
in Advanced Synthesis & Catalysis
Dubois N
(2013)
On DABAL-Me3 promoted formation of amides
in Tetrahedron
Hawner C
(2010)
Rhodium-catalyzed asymmetric 1,4-addition of aryl alanes to trisubstituted enones: binap as an effective ligand in the formation of quaternary stereocenters.
in Angewandte Chemie (International ed. in English)
Lee D
(2015)
Investigating Scale-Up and Further Applications of DABAL-Me 3 Promoted Amide Synthesis
in Organic Process Research & Development
Novak A
(2009)
Mapping the Mechanism of Nickel-Ferrophite Catalysed Methylation of Baylis-Hillman-Derived S N 2' Electrophiles
in European Journal of Organic Chemistry
Tang X
(2009)
Synthesis of a-Hydroxyallenes by Copper-Catalyzed S N 2' Substitution of Propargylic Dioxolanones
in European Journal of Organic Chemistry
Tang X
(2009)
Asymmetric conjugate additions to 1,1'-diactivated cyclic enones-a comparative study
in Tetrahedron: Asymmetry
Welker M
(2010)
Chemoselectivity as a delineator of cuprate structure in catalytic 1,4-addition of diorganozinc reagents to Michael acceptors.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Description | Liquid gallium can be used to alloy the surface of solid aluminium significantly imporving its reativity towards C-X insersion. This has been used to make various organoalanes. Additinally, some aluminium hydrides were prepared and used in organic synthesis |
Exploitation Route | metal activation, alane formation |
Sectors | Chemicals |
URL | http://www.nottingham.ac.uk/~pczsw/SWGroup/ |
Description | The reagents developed in this award appear to be being used in both academic and industrial settings. |
First Year Of Impact | 2014 |
Sector | Chemicals,Pharmaceuticals and Medical Biotechnology |
Description | Impact Acceleration |
Amount | £20,865 (GBP) |
Funding ID | EP/K503800/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start |
Title | DABAL-Me3 |
Description | An amide coupling reagent and air stable source of "Me-" |
Type Of Material | Technology assay or reagent |
Year Produced | 2007 |
Provided To Others? | Yes |
Impact | There are quite a few a web search of "DABAL-Me3" will reveal a representative selection. |
URL | https://www.youtube.com/watch?v=RfeaffoWajc |
Description | Aesica |
Organisation | Aesica Pharmaceuticals |
Country | United Kingdom |
Sector | Private |
PI Contribution | Development of DABAL-Me3 use on large scales. |
Collaborator Contribution | Access to lab facilities and advice. |
Impact | Publications (2). Folllow up funding (IAA) EP/K503800/1 |
Start Year | 2012 |
Description | Key Organics Ltd |
Organisation | Key Organics Ltd |
Country | United Kingdom |
Sector | Private |
PI Contribution | Use of DABAL-Me3 at scale and commercial sale at scale. |
Collaborator Contribution | Advice 'open innovation' partnership with ourselves and Aesica |
Impact | http://www.specchemonline.com/articles/view/when-silver-medal-sustainability-might-be-good-enough#.VryCfGfcsdV |
Start Year | 2012 |
Description | Uniqsis |
Organisation | Uniqsis Ltd |
Country | United Kingdom |
Sector | Private |
PI Contribution | Access to flow equipment (~k£40) and advice. |
Collaborator Contribution | Help developing DABAL-Me3 use in flow. |
Impact | Scale up development |
Start Year | 2014 |
Description | EPSRC impact aceleration meeting |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Regional |
Primary Audience | Policymakers/politicians |
Results and Impact | Forum for debate on effect of 'impact' |
Year(s) Of Engagement Activity | 2015 |
URL | https://www.epsrc.ac.uk/newsevents/news/impactaccelerationaccounts/ |