Research Projects

Among the mainstream practitioners, just atom-economics and sustainability are not impetus but it’s the essential imperatives alongside innovative and adaptable approaches for achieving ambitious transformations. In this context, electrochemistry is on the verge, of becoming one of the classical methods for the synthetic organic community to construct novel frameworks. As documented, the appeal and promises of electrochemistry to conceive an economical and persistently sustainable redox processes are nonetheless smoother than reagent-based methodologies. Electrochemical transformations inspired not only to transcend mere supplementing the unsustainable redox reagents but rather also, to forge new bonds with high selectivity and unique reactivity pathways for the synthesis of valuable chemical motifs. Undirected remote C−H bond functionalization is less advanced than directed methods due to the difficulty of achieving selectivity without chelation. This project aims to develop a unified metallaelectrocatalytic strategy for remote C–H functionalization by controlling transient intermediates to bypass the limitations of directing group-based approaches. Conventional C–H activation often requires covalently attached directing groups that restrict substrate scope, positional selectivity, and functional group tolerance. The proposed work seeks to overcome these constraints by employing high-valent metal species, open-shell radicals, and proton-coupled electron transfer (PCET) intermediates generated electrochemically under mild, redox-neutral conditions. The central hypothesis is that spatially and temporally controlled transient intermediates, modulated through metallaelectrocatalysis and ligand design, can enable site-selective C–H activation at otherwise unreactive or distal positions, including meta, γ-, δ-, or transannular sites. By precisely tuning electrochemical parameters, redox-active catalyst systems, and radical lifetimes, we aim to establish new reactivity paradigms for remote C–H bond activation that operate without preinstalled directing groups or external oxidants. Accordingly, leveraging our expertise in electro-organic synthesis and C-H functionalization herein, we propose work four mechanistically distinct but conceptually unified strategies for remote C–H functionalization via transient intermediate control. First, dual metallaelectrocatalyzed remote C–H activation of N-heterocycles will be developed, guided by substrate geometry and distance using a bifunctional Ni–Al–NHC complex that preorganizes the coordination environment and enables regioselective functionalization at the C3 or C7 position. Second, a dual metallaelectro(photo)-catalyzed approach will target adjacent C(sp3)–H bonds, enabling regio- and enantioselective difunctionalization of vicinal centers through sequential electrochemical and photochemical radical generation followed by stereocontrolled radical recombination. Third, PCET and hydride-induced transannular C(sp3)–H activation of alicyclic amines will be explored using electrochemical radical rebound strategies, where remote ring C–H bonds are selectively functionalized via transient radical intermediates modulated by anodic potential and redox-active metal catalysts. Finally, a metallaelectrocatalyzed self-immolative redox relay-driven meta-C–H functionalization of chalconoethers will be investigated, employing S/Se-radical cations or α-thioalkyl radicals to initiate through-bond electron transfer (TBET) or 1,5-hydrogen atom transfer (1,5-HAT), followed by meta-radical trapping and cross-coupling with strain-released bicyclo[1.1.0]butane-derived radicals. Central to this approach is the mechanistic exploitation of short-lived but selectively reactive species, whose lifetimes, reactivity, and spatial engagement with substrates can be tuned through current density, electrode potential, and catalyst design.