Hevia Group - Research

The Hevia group research focuses on new innovative polar organometallic chemistry, by preparing and structurally defining novel multicomponent reagents containing earth-abundant metals and developing their use (stoichiometrically and catalytically) in cornerstone synthetic methodologies (such as deprotonative metallation, metal-halogen exchange, alkylations, C-N and C-C coupling reactions). Spanning the interests of inorganic, synthetic organic, organometallic, catalytic and theoretical chemists, this chemistry offers vast untapped potential as it utilises cooperative effects between two different metals (or one metal with special assortment of ligands) that facilitate the opening up of new and unexpected reactivities/selectivities thus prompting the name synergic synthesis:

 

 

(i) Low polarity: metallation for chemoselective functionalisation of organic molecules

 

Our expertise in studying key organometallic intermediates from reaction solutions has enabled an in depth understanding of how to maximise efficiencies in C-H and C-X metal-exchange reactions, allowing stabilisation of hyper-sensitive organic anions as well as establishing new bimetallic approaches for chemoselective functionalisation of synthetically significant organic molecules;

Organometallics, 2015, 34, 2614. DOI: 10.1021/om501251q

Chem. Commun. 2014, 50, 12859. DOI: 10.1039/C4CC05305B

Chem. Sci. 2014, 5, 3552. DOI: 10.1039/C4SC01263A

Chem. Sci. 2013, 4, 1895. DOI: 10.1039/C3SC22326D

 

 

(ii) Sensitive anion trapping: applications in NHC functionalisation

 

Mixed-metal combinations operating in a concerted-cooperative or stepwise-cooperative manner have been exploited successfully for the functionalisation of N-heterocyclic carbenes NHC’s, establishing new ways to trap dianionic NHC’s fragments in reactions of unprecedented chemoselectivity and to access elusive main group abnormal NHC complexes.

Angew. Chem. Int. Ed. 2015, 54, 14075 DOI: 10.1002/anie.201507586

Chem. Sci. 2015, 6, 5719. DOI: 10.1039/C5SC02086G

Inorg. Chem. 2015, 54, 9201. DOI:  10.1021/acs.inorgchem.5b01638

Chem. Sci. 2013, 4, 4259. DOI: 10.1039/C3SC52101J

 

 

(iiii) Deep Eutectic Solvents and Salt Supported Organometallic Reagents

 

Assessing inorganic salt effects on earth-metal-rich organometallic reagents, we have demonstrated the formation of kinetically activated bimetallic reagents, which in some cases increases their resistance to air and moisture. Edging closer to realising an aerobic polar organometallic chemistry, we have shown the potential of DESs as green and biorenewable media in chemoselective alkylations of ketones using Grignard or organolithium reagents at room temperature under air!

Eur. J. Org. Chem. 2015, 6779. DOI: 10.1002/ejoc.201590088

Angew. Chem. Int. Ed. 2014, 53, 5969. DOI: 10.1002/anie.201400889

Angew. Chem. Int. Ed. 2014, 53, 2706. DOI: 10.1002/anie.201309841

 

 

(iv) Catalyic Applications of Cooperative Bimetallics

 

Preliminary studies probing the ability of sodium magnesiates to catalyse hydroamination/cyclotrimerization processes of isocyanates have revealed the first glimpses of the untapped potential of cooperative bimetallic ate reagents to effect catalytic transformations.

Chem. Commun. 2013, 49, 8659. DOI: 10.1039/C3CC45167D

Chem. Eur. J, 2011 17, 4470. DOI: 10.1002/chem.201002544

Eva Hevia Group, Department of Pure and Applied Chemistry, WestCHEM, University of Strathclyde,

295 Cathedral Street, Glasgow, G1 1XL, UK