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Abstract Toxic organic solvents and electrolytes, traditionally indispensable for electro‐organic synthesis, are now being reconsidered. In developing more sustainable electro‐organic synthesis, we've harnessed the aqueous micelles as solvents and electrolyte‐like structures when deformed under an electric field. The technology is showcased in synthetically highly valued hydrodefluorination reactions of difluorinated indoles. This mild electrosynthetic method produces monofluorinated unprotected indole scaffolds. Our approach minimizes waste and enhances atom economy, reducing reliance on expensive and hazardous solvents and electrolytes. The surfactant's potential for recycling was verified for two cycles. Cyclic voltammetry analysis has corroborated that PS‐750‐M micelles in water establish a more efficient platform for hydrodefluorination. Our technology simplifies the production of monofluorinated indoles, which are crucial for many drug‐like molecules. 

Abstract Herein, we developed the recyclable ligand‐free iridium (Ir)‐hydride based Ir⁰nanoparticles (NPs) for the first regioselective partial hydrogenation of P^V‐substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal‐surface‐bound hydrides, most likely formed from Ir⁰species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High‐resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X‐ray photoelectron spectroscopy confirmed the dominance of Ir⁰in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparingbis(diphenylphosphino)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐binaphthyl (H₈‐BINAP) and its derivatives without losing enantioselectivity during catalytic events.