Research

Chemical Sciences

Title :

Copper Complex-Light-Induced Homolysis and electrochemical Carbamoylation reactions via amidyl C(sp2)-H cleavage under Direct HAT

Area of research :

Chemical Sciences

Principal Investigator :

Dr. Anandhan Ramasamy, Madras University, Tamil Nadu

Timeline Start Year :

2024

Timeline End Year :

2027

Contact info :

Equipments :

Details

Executive Summary :

Carbamoylation reactions are a method for introducing amide functionality into organic molecules, with hydrogen atom transfer being a suitable reactive partner due to its high atom economy and low wastage. The development of carbamoyl intermediates from homolysis of C(sp2)-H formamide via hydrogen atom transfer is a powerful strategy for C-C, C-O, and C-N bonds formation. However, the development of visible light homolysis of C(sp2)-H formamide via HAT remains an unmet issue in the current literature. The Cu-complex-visible light-induced homolysis (VLIH) process is proposed as a key strategy for homolysis of C-H bond of formamide via direct HAT, generating nucleophilic carbamoyl radicals. Additionally, the Cu-complex is proposed as a key strategy for developing umpolung electrophilic carbamoyl cation by merging photo- and electrochemistry. Various carbamoylations will be carried out using nucleophilic addition carbamoyl radicals with various electrophilic substrates, including alkenes, alkynes, and ?,? unsaturated carbonyls. Carbamoylation reactions will be tested with 1,6-enynes with terminal alkynes followed by cascade cyclization. Carbamoylation will also be tested with electrophilic addition carbamoyl cations with various nucleophilic substrates. Under carbamoylation conditions, various cycloadditions will be performed using substrates of isocyanate cations and other reactive partners. The products obtained will be subjected to appropriate synthetic transformation into bio-active molecules, and screened for biological activities such as anti-bacterial, anti-fungal, and anti-cancer properties.

Total Budget (INR):

51,84,696

Organizations involved