Innovative DNA-based asymmetric catalysis
- Supervisor: Dr Stellios Arseniyadis
- Deadline: 30th June 2018
- Funding: QMUL (UK/EU only)
Applications are invited for a PhD studentship in Dr. Stellios Arseniyadis’ group at Queen Mary University of London.
The group is principally interested in developing new synthetic tools to attain high structural and functional complexity. These methods lie within the areas of organocatalysis, transition metal catalysis and, more recently, bio-hybride catalysis.
Bio-hybrid catalysts in which catalytically active metal complexes are bound to biopolymer scaffolds have proven to be remarkably versatile. A highly attractive feature of this new type of catalysts is that the chiral microenvironment, which is induced by binding a transition metal cofactor to a biopolymer, eliminates the need for an enantiopure metal complex. Another attractive feature of the hybrid approach is that the biopolymer scaffold and the transition-metal catalyst can both be optimized independently by genetic, evolutionary and synthetic methods. In the past two decades, a wide variety of artificial metalloenzymes have been designed and successfully applied to a plethora of enantioselective transformations. Interestingly however, while proteins have been widely used in the field of bio-hybrid catalysis, there are only a few examples reported in the literature which involve nucleic acids . Our group has recently joined the effort to develop synthetically useful DNA-based catalysts. In this context, we were able to show that double strand-DNA made from L nucleic acids instead of the natural occurring D nucleic acids could be used to reverse the selectivity of a given reaction in a reliable and predictable fashion . We also reported the first generation of a DNA-based catalyst bound to a cellulose matrix capable of achieving high levels of enantioselectivity on various Cu(II)-catalyzed asymmetric transformations . This chiral bio-hybrid material, which is commercially available, trivial to use and fully recyclable, was also implemented in a single-pass continuous-flow process affording fast conversions and high enantioselectivities at low catalyst loadings. More recently, we reported a new anchoring strategy based on the well-known minor groove-binder Hoechst 33258 . In the present project, we wish to extend the concept of DNA-based asymmetric catalysis by developing new and highly selective DNA-based catalytic systems with a special emphasis given to photocatalytic processes. The project yearns, through a careful design of DNA/ligand systems that will enable to develop highly enantioselective photocatalytic processes and ultimately apply them to the enantioselective synthesis of structurally complex natural products.
Techniques and Training: Dr. Arseniyadis’ group is based in the Joseph Priestley building which is fully equipped with state-of-the-art facilities, including high field NMR, EPR, AFM, IR and mass spectrometry, as well as HPLC and X-ray diffractometry. The successful student will receive complete training in a large number of organic chemistry techniques, in addition to developing transferable skills such as report writing, oral communication of results, project planning and organisation. All postgraduate researchers are part of the QMUL Doctoral College, which provides further high quality training in key skills such as critical thinking, teamwork and entrepreneurship. Candidates are expected to have a strong background and interest in synthetic organic chemistry. Prior experience in catalysis and multi-step synthesis is desirable but not required as the expertise of the group will provide an ideal training environment.
Environment: Queen Mary University of London is a member of the Russell group and is one of the leading research-focused institutions in the UK. All PhD students and post-doctoral researchers are part of the QMUL Doctoral College, which provides support with high-quality training and career development activities.
The studentship is open to UK and EU nationals. It will cover tuition fees and provide an annual tax-free maintenance allowance for 3 years at Research Councils UK rates (£16,777 in 2018/19).
Elgibility and Applying
Applications are welcome from outstanding students with or expecting to obtain a degree (equivalent to UK 1st or 2:1) in Chemistry. Previous experiences with asymmetric organocatalysis or biocatalysis are desirable but not essential.
For informal enquires please contact Dr. Arseniyadis and include your CV, a cover letter explaining eligibility and interest in the project and the contact details of two academic referees. Also don’t hesitate to visit Dr Stellios Arseniyadis’ current group website at https://blog.espci.fr/arseniyadis/ for an overview of his research. For the formal application, please submit an online application before the stated deadline.
 Duchemin, N.; Heath-Apostolopoulos, I.; Smietana, M.; Arseniyadis, S. Org. Biomol. Chem. 2017, 15, 7072.
 Wang, J.; Benedetti, E.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Vasseur, J.-J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Angew. Chem. Int. Ed. 2013, 52, 11546.
 Benedetti, E.; Duchemin, N.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Vasseur, J.-J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Chem. Commun. 2015, 51, 6076.
 Amirbekyan, K.; Duchemin, N.; Benedetti, E.; Joseph, R.; Colon, A.; Markarian, S. A.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Cossy, J.; Vasseur, J.-J.; Arseniyadis, S.; Smietana, M. ACS Catal. 2016, 6, 3096.
 Duchemin, N.; Benedetti, E.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Vasseur, J.-J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Chem. Commun. 2016, 52, 8604.