Development of novel desaturative strategies for aromatic synthesis

Background and Research Hypothesis.
Aromatic molecules are widespread among high-value materials like drugs and agrochemicals. A substantial fraction of these molecules contains more than one substituent, often placed in close proximity (ortho). The development of methods for the efficient assembly of poly-functionalized aromatic units is integral to both academic and industrial synthesis. A particularly relevant aspect is the development of processes that enable bypassing the limitation of either electrophilic and nucleophilic aromatic substitution reactivity.
The chemistry that will be developed here aims at providing novel synthetic platforms for the general and efficient preparation of aromatic derivatives from non-aromatic building blocks.

The approach.
We will attempt the development of desaturative methodologies based on the interplay of photoredox catalysis with cobalt catalysis for the formation of both electron rich and electron poor aromatics. In particular, we will target the conversions of cyclohexanones into phenols, piperidones into pyridines and cyclohexane-carbaldehydes in benzaldehydes.
This research project will require the utilization of an array of analytical techniques to understand and quantify the reaction outcomes and also to perform mechanistic studies. This will include NMR spectroscopy, mass spectrometry, UV/Vis absorption spectroscopy, electrochemistry and actinometry.

Novel physical sciences content.
This project will provide a novel approach to expediate the construction of high-value materials using unusual building blocks. The novel approach used and the mechanistic studies that will be performed will provide additional understanding in the fields of catalysis, synthetic chemistry, radical chemistry and cross-coupling in general.