Development of novel photochemical processes for C-N bond formation

Nitrogenated molecules are widespread among high-value materials like drugs and agrochemicals. A substantial fraction of these molecules contains an N-alkyl bond, which makes the development of methods for the efficient assembly of sp3 C-N bonds integral to both academic and industrial synthesis.
The chemistry that will be developed here aims at developing a synthetic platform enabling the general and efficient coupling of alkyl carboxylic acid derivatives with nitrogen electrophiles.

The approach.
We will attempt the development of a nickel catalyzed methodology for the coupling of activated carboxylic acids with activated nitrogen derivatives. We will need to prepare activated acids by condensation of the carboxylic acid unit with hydroxyphthalamide reagents and also prepare hydroxylamine derivatives as nitrogen coupling partners. With these materials in hand we will study the development of a process where nickel reduces the activated acid to the corresponding alkyl radical while sequentially activates the hydroxylamine by oxidative addition. This will enable a novel type of carbon-nitrogen bond formation via radical-organometallic pathway.
The 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 and UV/Vis absorption spectroscopy.

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.