Research Projects

Nitrogenous compounds form the cornerstone of life on this planet. From basic building blocks of biomolecules, to complex materials around us, almost everything has Nitrogen, be it in the form of functionalities, heterocycles, or ions. With the advent of photocatalysis, radical reactivity under mild conditions has come to the fore, providing new ways for the incorporation of various functionalities including those involving Nitrogen, into organic molecules. Thus, photogenerated Nitrogen-centred radicals (NCRs) is an exciting field of research that has the potential to compliment and improve upon the various C-N bond forming reactions that have been established conventionally since the beginning or synthetic organic chemistry. However, there are significant gaps in the existing research which needs to be addressed. Some of these are: • The pool of reagents currently available for NCR-generation is quite limited. • The reactivity of NCRs has been explored mostly in niche spaces as means of incorporating isolated N-containing functional groups. • Lack of merging/conjugation with other reactivity patterns available in photocatalysis such as Hydrogen Atom Transfer, and radical translocation. • The understanding of the factors governing persistence in case of NCRs is limited. • There is currently an empty space for designing reactions based on the difference in reactivity of transient and persistent NCRs which can lead to divergent N-incorporation. In the ensuing proposal we shall strategically design new reagents for NCR generation and use the different reactivity profiles of transient and persistent NCRs for diverse C-N bond forming processes. The detailed objectives are: • To strategically design and develop a new pool of reagents that can lead to transient and persistent NCRs under photocatalytic conditions. • To exploit the difference in reactivity of transient and persistent NCRs for diversified C-N bond formation reactions. • To generate NCR-containing synthons that contain strategically placed pendants for other value-added operations such as heteroannulation. • To merge NCR reactivity with other strategies such as radical translocation, Hydrogen atom transfer (HAT), group migration, etc. • To gain a clear understanding of the factors that decide the persistence of NCRs using experimental results and theoretical calculations. If the objectives of the current proposal are successfully achieved, the knowledge available in the fundamental aspects of NCR research will be significantly enhanced. We shall be able to significantly understand what controls the persistence and differing behaviours of NCRs in terms of reactivity. In its core, the current proposal contains a wide blueprint for the tactical utilization of NCRs for a diverse array of reactions. The merging of NCR reactivity with secondary reactivity sites leads to different classes of value-added compounds. As the proposal blankets a variety of heterocycle construction, it has potentially valuable applications in both academia and industry as they are widely found in pharmaceuticals, agrochemicals and functional materials. With successful industrial collaboration there is a genuine possibility for converting our small-scale synthesis of these valuable heterocycles into pilot-scale projects. This is a rapidly growing field which demands considerable training in a number of specialized methods. Hence, the project can potentially impact in guiding the youth towards cutting-edge chemistry and creating a highly skilled workforce in fine chemicals and pharmaceutical development, leading to betterment of the society. Keeping these ideas in mind, we firmly believe that the successful culmination of this project is a step towards an "Atmanirbhar Bharat".