(BBSRC DTP) Photoenzymatic C–H radical alkylation of arenes using S-adensoyl methionine analogues

In a future where sustainability will be a key driver, we must synthesise high value molecules from simple feedstocks in an expedient fashion. So called ‘C–H activation’ will be a key strategy in future synthesis as it allows C–H bonds present in almost every feedstock chemical to be converted to, for example, more valuable C–C bonds. Unfortunately, most methods for C–H activation currently involve expensive/toxic metal catalysts and controlling the selectivity for a particular C–H bond, in feedstocks where there are many, remains a grand challenge.
In this project, we propose that the marriage of visible light photocatalysis and biocatalysis will allow the selective formation of important C–C bonds at the expense of C–H bonds in aromatic feedstocks, thus facilitating the sustainable synthesis of high-value products of industrial relevance. Our approach will use enzymes to control the selectivity of C–H functionalization, organic photocatalysts to generate radicals, and bioinspired sulfonium salts as radical precursors. A suite of sulfonium salts will be accessed using either chemo- or bio-catalysis and will allow a wide range of high value products to be prepared using the proposed photoenzymatic approach.
Two leaders in their respective fields will join forces for the first time and pool their complementary expertise in supervising the project. The Procter group is world-leading in the chemistry of sulfonium salts1 and radicals2 and has recently reported a metal-free photocatalyzed C–H functionalized of aromatic substrates using sulfonium salts.3 The Micklefield group is world-leading in the use of S-adenosylmethionine (SAM) analogues – sulfonium salts used by Nature – in biocatalysis and has recently reported several applications of SAM analogues in biology.4
The project is ideally suited to a synthetic chemist with an interest in biocatalysis. A multidisciplinary supervisory team of internationally-leading scientists will deliver a unique training programme.

Procter Group Research: http://proctergroupresearch.com
Micklefield Group Research: http://www.micklefieldlab.chemistry.manchester.ac.uk
Hay Group Research: https://www.research.manchester.ac.uk/portal/sam.hay.html

Entry Requirements:
Applicants must have obtained, or be about to obtain, at least an upper second class honours degree (or equivalent) in a relevant subject.

UK applicants interested in this project should make direct contact with the Principal Supervisor to arrange to discuss the project further as soon as possible. International applicants (including EU nationals) must ensure they meet the academic eligibility criteria (including English Language) as outlined before contacting potential supervisors to express an interest in their project. Eligibility can be checked via the University Country Specific information page (https://www.manchester.ac.uk/study/international/country-specific-information/).

If your country is not listed you must contact the Doctoral Academy Admissions Team providing a detailed CV (to include academic qualifications – stating degree classification(s) and dates awarded) and relevant transcripts.

Following the review of your qualifications and with support from potential supervisor(s), you will be informed whether you can submit a formal online application.

To be considered for this project you MUST submit a formal online application form - full details on how to apply can be found on the BBSRC DTP website www.manchester.ac.uk/bbsrcdtpstudentships

Equality, diversity and inclusion is fundamental to the success of The University of Manchester, and is at the heart of all of our activities. The full Equality, diversity and inclusion statement can be found on the website https://www.bmh.manchester.ac.uk/study/research/apply/equality-diversity-inclusion/