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Application of DNA-based asymmetric catalysis to natural product synthesis

Bio-inspired catalysis is emerging as a particularly attractive tool, which combines homogeneous catalysis and biocatalysis. Interestingly, while proteins have been wildly used to catalyse a variety of synthetic transformations in a highly enantioselective and effective fashion, there are only a few examples reported in the literature which involve nucleic acids. This is particularly noteworthy considering that the right-handed double helix of DNA is one of the most ubiquitous and elegant examples of chirality in nature. Surprisingly, only a few research groups have tried to exploit this property. As a matter of fact, the rational design for DNA based asymmetric catalysis has so far mostly been limited to the use of Cu in the presence of achiral intercalative ligands. The challenge in DNA-based asymmetric catalysis is to perform a reaction in the vicinity of the helix in order to enable chiral discrimination. By analogy with the hybrid metalloenzymes, DNA-based asymmetric catalysts should incorporate a small-molecule catalyst anchored in a covalent, dative, or non covalent yet kinetically stable fashion to the DNA.

The first example of a DNA-based catalyst featuring a non-chiral ligand bound to DNA in a non-covalent fashion was reported in 2005 and consisted of a catalytically active Cu(II) complex linked to a DNA-intercalating acridine through a spacer. This biohybrid was initially used to catalyze asymmetric Diels-Alder reactions between, but was later used in various other asymmetric transformations including asymmetric Michael additions, Friedel-Crafts alkylations as well as fluorinations. By taking advantage of the unique structural features of L-DNA, mirror image of the natural D-DNA, we recently described the first example of left-helical enantioselective induction in the field of DNA-based asymmetric catalysis. As a matter of fact, this approach is the only one that allows a reliable and predictable access to both enantiomers for any given reaction (see Angew. Chem. Int. Ed. 2013, 52, 11546-11549). Following these initial results, we also developed a robust, trivial to use and recyclable cellulose supported DNA-based catalyst that offers high levels of enantioselectivity on various Cu(II)-catalyzed asymmetric reactions including Friedel–Crafts alkylations and Michael additions (see Chem. Commun. 2015, 51, 6076-6079).

In the present project, we envision to expend the scope of DNA-based asymmetric catalysis by developing new synthetic transformations with a special emphasis given to asymmetric electrocyclization and cycloaddition processes. Most importantly, we wish to apply these methods to the synthesis of various relevent natural products.

Applications are invited for a fully-funded PhD studentship in the Arseniyadis group at Queen Mary University of London. The position covers both tuition fees and a maintenance stipend. 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.

Please contact Dr Stellios Arseniyadis for more information. Also don’t hesitate to visit Dr Stellios Arseniyadis’ current group website for an overview of his research.

To apply, go to our online application page and send a complete CV and a cover letter outlining your qualifications and previous research experience.

Informal enquiries about the project can be made by email to Dr Stellios Arseniyadis.

Eligibility

In order to qualify for funding from Ciência sem Fronteiras, applicants must be Brazilian nationals and are required to have at least an upper second class degree and a masters degree in a related discipline from a top university anywhere in the world. For more information visit the Ciência sem Fronteiras eligibility pages.

Expertise in psychology, management and economics is desirable.

International students must provide evidence of proficient English language skills, see our entry requirements page for further information.

Application process

All international students must provide evidence of proficient English language skills; see our entry requirements page for further information.

Ciência sem Fronteiras

Potential candidates should contact Dr Stellios Arseniyadis and submit their CV (including details of two referees) and a cover letter explaining their eligibility and interest in this project.

Applications to Queen Mary and Ciência sem Fronteiras are accepted all year round but we encourage you to contact Dr Arseniyadis as soon as possible.

If you are successful we will give you an offer on the condition that you are given a funding award from Ciência sem Fronteiras. When you have received a conditional offer, apply directly to Ciência sem Fronteiras.

China Scholarship Council

Applicants should be Chinese nationals and are required to have at least an upper second class degree and a masters degree in a related discipline from a top university anywhere in the world.

Potential candidates should contact Dr Stellios Arseniyadis and submit their CV (including details of two referees) and a cover letter explaining their eligibility and interest in this project.

If you are successful we will give you an offer on the condition that you are given a funding award from the China Scholarship Council. When you have received a conditional offer, apply directly to the China Scholarship Council.

CONACYT

Applicant requirements are listed on the CONACYT foreign scholarship pages.

Potential candidates should contact Dr Stellios Arseniyadis and submit their CV (including details of two referees) and a cover letter explaining their eligibility and interest in this project.

Applications to Queen Mary are accepted all year round but we encourage you to contact Dr Arseniyadis as soon as possible. If he agrees to take your application further you will be required to submit an online application.

If you are successful we will give you an offer on the condition that you are given a funding award from CONACYT.

When you have received a conditional offer from us, you should apply directly to CONACYT.

References:

Wang, J.; Benedetti, E.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Vasseur, J. J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Angew. Chem. Int. Ed. Engl. 2013, 52, 11546-11549.

Benedetti, E.; Duchemin, N.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Vasseur, J. J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Chem. Commun. 2015, 5

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