Research

Chemical Sciences

Title :

Electrochemical Generation of Ketyl Radicals Via Cathodic Reduction and Their Further Functionalizations

Area of research :

Chemical Sciences

Principal Investigator :

Dr. Nilima Periyadarsini Mishra, Indian Institute Of Technology (IIT) Ropar, Punjab

Timeline Start Year :

2022

Timeline End Year :

2024

Contact info :

Details

Executive Summary :

The modern organic synthesis is hunted for the growth of greener and environmentally viable techniques to synthesize highly functionalized motifs. Amongst all greener protocols, electro-organic reactions are now regarded as one of the most significant and convenient methods for the synthesis of organic molecules by utilizing electrochemical oxidation and reduction reactions. Also, the use of electrons as a “traceless” reagent in place of commonly used reactive oxidants/reductants can diminish the risk, cost, waste production and promote the atom/step efficiency. As the gracious features of electrochemical reactions gradually uncovered and studied, several scientific communities believed that electro-organic reactions have become a growing area of research in the coming era. The recent obsession towards electro-organic synthesis has already been made a numerous works i.e, “(un)divided cell”, “indirect electrolysis”, “constant-current/potential electrolysis” and so on. The overall electro-organic reactions can be classified as anodic oxidation, cathodic reduction and paired electrolysis based on the electrode where the reaction occurred. Recently, anodic oxidation reactions are well explored i.e, dehydrogenative C-C or C-X cross coupling reaction, cyclization reaction, metal assisted selective C-H bond activation and so on. Like anodic oxidation reaction, cathodic reduction reactions also have diverse applications and behave as safer sacrificial reductants under milder conditions which can be used as an attractive alternative to the traditional protocols. Several reactions were developed such as the reduction of unsaturated hydrocarbons, heteroatom-containing carbon based unsaturated system, C-hetero or C-C polar/strained bonds and hetero-hetero linkages by using the cathodic reduction reactions. In spite of the clear conceptual applications, high efficiency and selectivity of this reductive transformation at the cathode appears less popular. Along with this, the ketyl radicals are treated as valuable reactive intermediates for the construction of complex and functionalized products from carbonyl substrates. A decade ago, the ketyl radicals were generated by different classical methods and by using photoredox catalysts. Furthermore, single electron transfer, proton-coupled electron transfer, hydrogen atom and halogen atom abstraction have also been used to access ketyl radicals. It is worth mentioning that the utility of ketyl radicals is highly exemplified by their privileged significance in C-C bond formation, ketyl-olefin coupling reactions, total synthesis of natural products, in enzymatic reactions and in polymerizations which deliver high value products. Though ketyl radicals have wide application in organic reactions, but till now the formation of ketyl radicals by using cathodic reduction is not reported yet. So that, PI envisioned for the electrochemical generation of ketyl radicals via cathodic reduction for further functionalization.

Organizations involved