Research Projects

This proposal aims to develop a cost-effective and mild reaction methods for CO₂ utilization in the organic synthetic chemistry by bypassing kinetically challenging direct electron transfer to CO₂ process (Chem 2020, 6, 2658–2672). In this proposed strategy, the well-known photo catalyzed PCET method will be used with organic photocatalysts to avoid the use of any transition metal (Acc. Chem. Res. 2016, 49, 1546−1556). Currently, this PCET method has been used for decarboxylative alkyl radical generation and functionalization with using an organic photocatalyst (Angew. Chem., Int. Ed. 2020, 59, 7921-7927). Although this method has tremendous potential to abstract proton and electron from the substrate at a single photoexcitation, but this method only has been examined with aliphatic carboxylic acid substrates. In this proposed method, at first bi-carbonate anion will be prepared from CO2 then that photoinduced PCET method will be used to produce carbonate radical anion which will be further utilized in various kind of organic catalytic transformations. Firstly, photo-catalytically generated carbonate radical anion will be taken to direct functionalization with unsaturated substrates for cyclic carbonate preparation. Secondly, carbonate radical anion will be used as a strong oxidant to produce other nucleophile based radical and they will be functionalized to aromatic or any other unsaturated system. In this second type of reactions carbonate radical anion will not be used as a substrate. These proposed methods can be very useful in the development of a new strategy to use CO₂ in organic synthesis by exploring the reactivity of carbonate radical anion which has not been yet explored in the field of photocatalysis. A thorough mechanistic investigation with the help of experimental and computational tools will be carried out to understand the reaction pathway.