Catalytic arene functionalization with nucleophilic heavier alkaline earth reagents

The Centre for Sustainable Chemical Technologies (CSCT) at the University of Bath has now launched a new joint PhD programme with Monash University, Australia. The Bath Monash Global PhD Programme will have its first intake in October this year.

This project is one of a number that are in competition for up to four funded studentships. More details are available here: http://www.csct.ac.uk/study-with-us/.

Home institution: University of Bath
Supervisor at Bath: Professor Michael Hill (lead)
Supervisor at Monash: Professor Cameron Jones

The direct addition of aromatic C-H bonds to unsaturated substrates (alkenes or alkynes) would provide an atom-economical strategy for the synthesis of valuable functionalised aromatic molecules. Although limited reports of hydroarylation chemistry have appeared since the 1980s, this reactivity typically remains in the realm of precious metal (e.g. Pd, Pt, Ir) catalysis. This PhD project will build directly on the recent discovery in the Hill group that alkyl and hydride derivatives of calcium (e.g. 1), one the most earth abundant and non-toxic elements, can effect the displacement of hydride from benzene to provide direct nucleophilic access to alkyl benzene derivatives (Scheme 1). Although, hypothetically, this chemistry may be readily extended to a catalytic regime, the scope this reactivity is limited by the solution instability of the -diketiminate complexes toward Schlenk equilibration to inactive and/or insoluble species.

The Hill and Jones groups have previously reported that the synthesis of unusual 3-coordinate magnesium hydrides may be achieved through judicious ligand design. This PhD project will exploit this joint expertise to devise novel heteroleptic hydride derivatives of calcium and its heavier congeners, strontium and barium, (e.g. 2, Scheme 1), which will display enhanced stability toward deleterious Schlenk equilibria. The reactivity of the new compounds will be studied to assess and develop their ability to (a) activate sp2 and sp3 C-H bonds; (b) enable further completely unprecedented catalytic transformations, including the hydroarylation of hydrocarbon arenes and alkenes and the catalytic synthesis of valuable bi- and polyaryl species. The student will be trained to experimentally investigate the mechanisms of any new transformations, which will be assessed computationally through DFT methods by Prof. L. Maron (University of Toulouse), who has a strong history of collaboration with both the Bath and Monash research groups.

Applications:

We invite applications from Science and Engineering graduates who have, or expect to obtain, a first or upper second class degree and have a strong interest in Sustainable Chemical Technologies.

You may express an interest in up to three projects in order of preference. See the CSCT website for more information: http://www.csct.ac.uk/study-with-us.

Please submit your application to the Home institution of your preferred project. However, please note that you are applying for a joint PhD programme and applications will be processed as such.

If this is your preferred project, apply using Bath’s online application form:
https://samis.bath.ac.uk/urd/sits.urd/run/siw_ipp_lgn.login?process=siw_ipp_app&code1=RDUCH-MO01&code2=0001.
Please quote ‘Bath Monash PhD studentship’ in the Finance section and the lead supervisor(s)’ name(s) and project title(s) in the ‘Your research interests’ section. More information on applying to Bath may be found here:
https://www.bath.ac.uk/guides/how-to-apply-for-doctoral-study/

If the Home institution of your preferred project is Monash, apply here: https://docs.google.com/forms/d/e/1FAIpQLSd4RT7A62PF6DSqLQLNFBUltFIHv1Cf12oI_CKY_Op8-k3XPw/viewform

Enquiries about the application process should be sent to [Email Address Removed].