This project will involve work in the catalytic C–H activation area. While C−H activation has the potential to revolutionize synthetic chemistry, by allowing access to complex structures by functionalization of the ubiquitous C−H bonds, several important challenges still remain for this potential to be realized. Indeed, most C−H activation methods suffer from the need for harsh conditions, resulting in limited applicability and unsuitability towards molecules containing delicate functional groups. However, most pharmaceuticals, and in general biologically active molecules, contain delicate functional groups. The current project is based on a recent breakthrough in the Larrosa group that led to a new class of Ru-catalysts operating under very mild conditions (Nature Chemistry, 2018, 724). In this project we aim at designing and developing a second generation Ru-catalyst from this platform, capable to carry out a variety of C−H functionalizations in complex molecules with biological activity. Methodology development will be mechanistically driven, utilizing state-of-the-art mechanistic investigation approaches.
The student will become proficient in organic synthesis, organometallic chemistry and in the design and development of complex multi-metallic catalytic cycles, as well as in the use of tools such as DFT and kinetics in order to study reaction mechanisms. Transferable and leadership skills such as reporting of results orally and in writing, time management, project planning and management will be developed.
Academic background of candidates:
Applicants are expected to hold, or about to obtain, a minimum upper second class undergraduate degree (or equivalent) in Chemistry. A Masters degree in organic or organometallic chemistry and/or equivalent experience is desirable.
Contact for further Information:
Prof. Igor Larrosa
[email protected] https://personalpages.manchester.ac.uk/staff/igor.larrosa/index.html
Funding Notes
This is a 3.5 year studentship funded by an ERC Grant. The funding will cover tuition fees and stipend (£15,285 in 2020-21)
Open to all applicants.
We expect the programme to commence in September 2020
References
“Cyclometallated ruthenium catalyst enables late-stage directed arylation of pharmaceuticals”, Marco Simonetti, Diego M. Cannas, Xavier Just-Baringo, Iñigo J. Vitorica-Yrezabal and Igor Larrosa Nature Chem. 2018, 10, 724-731.
“Benzoate cyclometallation enables oxidative addition of haloarenes at a Ru(II) center”, Marco Simonetti, Rositha Kuniyil, Stuart A. Macgregor and Igor Larrosa J. Am. Chem. Soc. 2018, 140, 11836–11847.
“Ag(I)-C–H Activation Enables Near-Room Temperature Direct α-Arylation of Benzo[b]thiophenes”, Chiara Colletto, Adyasha Panigrahi, Jaime Fernandez-Casado and Igor Larrosa J. Am. Chem. Soc. 2018, 140, 9638-9643
“Ag(I)-catalyzed C-H activation: the role of the Ag(I) salt in Pd/Ag mediated C-H arylation of electron-deficient arenes”, Daniel Whitaker, Jordi Burés and Igor Larrosa J. Am. Chem. Soc. 2016, 138, 8384-8387.
“Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides”, Marco Simonetti, Gregory J. P. Perry, Xacobe C. Cambeiro, Francisco Juliá-Hernández, Jude N. Arokianathar and Igor Larrosa J. Am. Chem. Soc. 2016, 138, 3596-3606.
