Kwangmin Shin

Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups s

New horizons in the utility of azides: The rhodium-catalyzed intermolecular direct CH amination of arenes with alkyl azides provides a convenient route to N-alkyl anilines (see scheme; DG=directing group). Alkyl azides with a wide range of functional groups reacted readily with various substrates, including benzamides, aromatic ketones, and flavones. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed an

Reported herein is the development of Cp*Ir(III)-catalyzed direct C-H arylation of arenes and alkenes using aryldiazonium tetrafluoroborates, the use of which as an aryl precursor and also as an oxidant via C-N2 bond cleavage was a key to success in achieving a mild and external oxidant-free procedure. Mechanistic experiments and DFT calculations revealed the turnover-limiting step to be closely related to the formation of an Ir(V)-aryl intermediate rather than the presupposed C-H cleavage. Unde

Iridium-catalyzed regioselective C-7 amination of indolines has been achieved with organic azides as a facile nitrogen source. The developed procedure is convenient to perform even at room temperature and applicable to a wide range of substrates with high catalytic activity. Various types of organic azides (sulfonyl, aryl, and alkyl derivatives) were all successfully reacted under the present conditions as the viable reactant. Furthermore, indoline substrates bearing easily removable N-protectin

The dual reactivity of acyl azides was utilized successfully in C-H activation by the choice of catalyst systems: while selective C-C amidation was achieved under thermal Rh catalysis, a Ru catalyst was found to mediate direct C-N amidation also highly selectively. Investigations of the mechanistic dichotomy between two catalytic systems are also presented.

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

Neue Horizonte für Azide: Die Rhodium-katalysierte intermolekulare direkte C-H-Aminierung von Arenen mit Alkylaziden bietet eine bequeme Route zu N-Alkylanilinen (siehe Schema; DG=dirigierende Gruppe). Alkylazide mit verschiedensten funktionellen Gruppen reagierten bereitwillig mit diversen Substraten wie Benzamiden, aromatischen Ketonen und Flavonen.

Abstract The tris(pentafluorophenyl)boron‐catalyzed domino hydrosilylation of substrates carrying unsaturated functionalities in a proximal arrangement is presented to produce silacycles. Excellent levels of efficiency and selectivity were achieved in the cyclization by the deliberate choice of the hydrosilane reagents. The key to successful cyclic hydrosilylation is the reactivity enhancement of the second intramolecular hydrosilylation by a proximity effect. Not only dienes but also enones, en

Herein, we report an electrocatalytic hydrofluorination of aryl-substituted alkenes with a nucleophilic fluorine source. The merger of palladium catalysis with electrooxidation enables the transformation of various substrates ranging from styrenes to more challenging α,β-unsaturated carbonyl derivatives to the corresponding benzylic fluorides. This method can also be applied to the late-stage modification of pharmaceutical derivatives. Mechanistic studies suggest that the generation of a high-va

Acyl fluorides have emerged as efficient acyl group donors, but these attractive reagents have rarely been utilized in transition-metal-catalyzed hydroacylation. Herein we report a nickel hydride-catalyzed hydroacylation of aryl alkenes using aroyl fluorides. The reaction proceeds without recourse to an exogenous ligand under mild conditions. The synthetic utility of the present method is demonstrated by the glovebox-free, gram-scale reaction and the late-stage derivatization of complex molecule

Abstract Acyl fluorides, carbamoyl fluorides and fluoroformates have been employed as efficient reagents in a number of organic syntheses. Their application in catalytic transformations, however, began to be explored in the early 2000s. Recently, these reagents have increasingly gained attention owing to their unique reactivity in diverse catalytic systems. This review aims to overview the advancements in the development of catalytic processes, including transition‐metal catalysis, organocatalys

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

An electrooxidative palladium-hydride catalytic system has been developed for the hydrofluorination of β-aryl-α,β-unsaturated amides using various nucleophilic fluorine sources, including Me₄NF, Me₄NF·<i>t</i>AmylOH, <i>n</i>Bu₄NF·(<i>t</i>BuOH)₄, CsF, and KF. By avoiding hazardous HF-based reagents, this electrocatalytic protocol offers a safer and more practical route for the formal conjugate addition of fluoride to β-aryl-α,β-unsaturated amides, ena