Hyunwoo Kim

Azetidines are prominent structural scaffolds in bioactive molecules, medicinal chemistry, and ligand design for transition metals. However, state-of-the-art methods cannot be applied to intramolecular hydroamination of allylic amine derivatives despite their underlying potential as one of the most prevalent synthetic precursors to azetidines. Herein, we report an electrocatalytic method for intramolecular hydroamination of allylic sulfonamides to access azetidines for the first time. The merger

We disclose a general electrocatalytic hydroetherification for modular synthesis of alkyl aryl ethers by utilizing a wide range of alkenes and phenols. The integration of the two involves an electrochemically instigated cobalt-hydride-catalyzed radical-polar crossover of alkenes that enable the generation of key cationic intermediates, which could readily be entrapped by challenging nucleophilic phenols. We highlight the importance of precise control of the reaction potential by electrochemistry

An electrochemical method that provides an operationally simple synthesis of masked <italic>syn</italic> -1,2-diols from styrenes and DMF has reported. The TFA ion is engaged in the formation of a key intermediate, which gives rise predominantly to <italic>syn</italic> -selectivity.

The difluoromethyl group (CF 2 H) serves as an essential bioisostere in drug discovery campaigns according to Lipinski’s Rule of 5 due to its advantageous combination of lipophilicity and hydrogen bonding ability, thereby improving the ADME properties. However, despite the high prevalence and importance of vicinal hydrogen bond donors in pharmaceutical agents, a general synthetic method for doubly difluoromethylated compounds in the vicinal position is absent. Here we describe a copper-electroca

Abstract Due to its superior ability in controlling pharmaceutical activity, the installation of difluoromethyl (CF 2 H) functionality into organic molecules has been an area of intensive research. In this context, difluoromethylation of C−C π bonds mediated by a CF 2 H radical have been pursued as a central strategy to grant access to difluoromethylated hydrocarbons. However, early precedents necessitate the generation of oxidative chemical species that can limit the generality and utility of t

The difluoromethyl (−CF 2 H) group has gained considerable significance in synthetic and medicinal chemistry due to its ability to modulate molecular properties, including electronic effects and hydrogen-bonding capability. Traditional difluoromethylation methods often require specialized reagents and demanding reaction conditions, potentially limiting their applicability across diverse substrates. Electrochemical difluoromethylation has emerged as an alternative approach that enables the in sit

We described a silver(I)-mediated intramolecular oxidative C-H amination that enables the construction of assorted 1<i>H</i>-indazoles that are widely applicable in medicinal chemistry. The developed amination was found to be efficient for the synthesis of a variety of 3-substituted indazoles that are otherwise difficult to be synthesized by other means of C-H aminations. Preliminary mechanistic studies suggested that the current amination proceeds via single electron transfer (SET) mediated by

Abstract We describe a catalyst, oxidant, and coupling‐reagent free strategy to access 4‐membered heterocycles, representing a unique example of visible‐light triggered intramolecular cyclization of propargylic alcohols and amines to access oxetanones and azetidinones respectively. Despite the direct 4‐endo‐dig cyclization from these starting materials has proven to be unfavorable, the formation of key p ‐quinone methide intermediacy allows an efficient bypass for regioselective 4‐exo‐trig cycli

We present highly efficient and operationally simple synthetic methods for 1,2-aminoalcohols via electroreductive cross aza-pinacol coupling between N -acyl diarylketimines and aldehydes. Preliminary mechanistic studies including cyclic voltammetry and density functional theory (DFT) calculations suggest that the reaction is instigated by selective electrochemical single electron transfer (SET) of N -acylketimines. The developed electrochemical protocol is compatible to biorelevant functional gr

The catalytic hydrofunctionalization of alkenes with nucleophiles via the generation of carbocationic intermediates has been extensively studied as an efficient strategy for the regioselective installation of functional groups on alkene feedstocks. However, since the established methods are confined to functionalization of the position where the alkene is originally located, it is highly desirable to develop a broadly applicable catalytic hydrofunctionalization platform that offers an alternativ

We present a catalyst-free strategy that combines photochemical and electrochemical activation to unlock unique reactivity in otherwise less reactive molecules. Photochemical excitation generates intermediates that can undergo electrochemical oxidation to form highly electrophilic species that can engage weak nucleophiles, enabling the synthesis of diverse heterocycles under mild conditions. Mechanistic studies, including voltammetric, spectroscopic, and computational analyses, suggest that a li

The selection of electrode material is a critical factor that determines the selectivity of electrochemical organic reactions. However, the fundamental principles governing this relationship are still largely unexplored. Herein, we demonstrate a photoelectrocatalytic (PEC) system as a promising reaction platform for the selective radical-radical coupling reaction owing to the inherent charge-transfer properties of photoelectrocatalysis. As a model reaction, the radical trifluoromethylation of ar

The selection of electrode material is a critical factor that determines the selectivity of electrochemical organic reactions. However, the fundamental principles governing this relationship are still largely unexplored. Herein, we demonstrate a photoelectrocatalytic (PEC) system as a promising reaction platform for the selective radical–radical coupling reaction owing to the inherent charge-transfer properties of photoelectrocatalysis. As a model reaction, the radical trifluoromethylation of ar

We disclose a general electrocatalytic hydroetherfication for modular synthesis of alkyl aryl ethers by utilizing a wide range of alkenes and phenols. The integration of the two involves an electrochemically instigated cobalt-hydride catalyzed radical–polar crossover of alkenes that enables the generation of key cationic intermediates, which could readily be entrapped by challenging nucleophilic phenols. We highlight the importance of precise control of the reaction potential by electrochemistry