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Herein, a straightforward and efficient route for the construction of dual α,β-C(sp3)–H functionalized cyclic N-aryl amines using a combination of electrocatalysis and iron catalysis is disclosed. This method is achieved by multiple single electron oxidations and is carried out in an operationally simple manner with high chemo- and site-selectivity, setting the stage for the challenging multiple site selective C–H functionalization. The mechanism is supported by a variety of experimental probes and theoretical investigations, including cyclic voltammetry tests, a bipolar ultramicroelectrode (BUME) methodology combined with nano-electrospray ionization mass spectrometry, and density functional theory calculations. [ABSTRACT FROM AUTHOR]

Herein, a direct, metal‐free, and site‐selective electrochemical C−H carboxylation of arenes by reductive activation using CO2 as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo‐ and regioselectivity, setting the stage for the challenging site‐selective C−H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C−H carboxylation of various challenging arenes worked well in this approach, including electron‐deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst‐free, metal‐free and base‐free, which makes it extremely attractive for potential applications. [ABSTRACT FROM AUTHOR]

Herein, a direct, metal‐free, and site‐selective electrochemical C−H carboxylation of arenes by reductive activation using CO2 as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo‐ and regioselectivity, setting the stage for the challenging site‐selective C−H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C−H carboxylation of various challenging arenes worked well in this approach, including electron‐deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst‐free, metal‐free and base‐free, which makes it extremely attractive for potential applications. [ABSTRACT FROM AUTHOR]

Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of monohydrosilanes via an intramolecular hydrosilylation strategy. This protocol is suitable for the synthesis of five‐ and six‐membered cyclic monohydrosilanes, including a class of chiral oxasilacycles, with excellent diastereo‐, regio‐, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol % which makes this one of the most efficient methods to access chiral monohydrosilanes. Mechanistic studies and DFT calculations indicate this Rh‐catalyzed intramolecular asymmetric hydrosilylation reaction might proceed via a Chalk–Harrod mechanism, and the enantio‐determining step was predicted to be oxidative addition of Si−H bond. [ABSTRACT FROM AUTHOR]

A direct metal-free, base-free, and site-selective electrochemical C-H carboxylation of arenes by reductive activation using CO SB 2 sb as an economic and abundant carboxyl source was developed. C-H Carboxylation, CO2 Valorization, Carbon Dioxide, Electroreduction, Selectivity Keywords: C-H Carboxylation; CO2 Valorization; Carbon Dioxide; Electroreduction; Selectivity EN C-H Carboxylation CO2 Valorization Carbon Dioxide Electroreduction Selectivity 1 1 1 01/11/23 20230116 NES 230116 B A site-selective electrochemical b C-H carboxylation of arenes with CO SB 2 sb is reported by Youai Qiu and co-workers in their Research Article (e202214710). [Extracted from the article]

A direct metal-free, base-free, and site-selective electrochemical C-H carboxylation of arenes by reductive activation using CO SB 2 sb as an economic and abundant carboxyl source was developed. C-H Carboxylation, CO2 Valorization, Carbon Dioxide, Electroreduction, Selectivity Keywords: C-H Carboxylation; CO2 Valorization; Carbon Dioxide; Electroreduction; Selectivity EN C-H Carboxylation CO2 Valorization Carbon Dioxide Electroreduction Selectivity 1 1 1 01/11/23 20230116 NES 230116 B A site-selective electrochemical b C-H carboxylation of arenes with CO SB 2 sb is reported by Youai Qiu and co-workers in their Research Article (e202214710). [Extracted from the article]

Herein, a direct, metal‐free, and site‐selective electrochemical C−H carboxylation of arenes by reductive activation using CO2 as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo‐ and regioselectivity, setting the stage for the challenging site‐selective C−H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C−H carboxylation of various challenging arenes worked well in this approach, including electron‐deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst‐free, metal‐free and base‐free, which makes it extremely attractive for potential applications. [ABSTRACT FROM AUTHOR]

Herein, a direct, metal‐free, and site‐selective electrochemical C−H carboxylation of arenes by reductive activation using CO2 as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo‐ and regioselectivity, setting the stage for the challenging site‐selective C−H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C−H carboxylation of various challenging arenes worked well in this approach, including electron‐deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst‐free, metal‐free and base‐free, which makes it extremely attractive for potential applications. [ABSTRACT FROM AUTHOR]

Herein, a direct, metal-free, and site-selective electrochemical C-H carboxylation of arenes by reductive activation using CO 2 as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo- and regioselectivity, setting the stage for the challenging site-selective C-H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C-H carboxylation of various challenging arenes worked well in this approach, including electron-deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst-free, metal-free and base-free, which makes it extremely attractive for potential applications., (© 2022 Wiley-VCH GmbH.)

Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of monohydrosilanes via an intramolecular hydrosilylation strategy. This protocol is suitable for the synthesis of five- and six-membered cyclic monohydrosilanes, including a class of chiral oxasilacycles, with excellent diastereo-, regio-, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol % which makes this one of the most efficient methods to access chiral monohydrosilanes. Mechanistic studies and DFT calculations indicate this Rh-catalyzed intramolecular asymmetric hydrosilylation reaction might proceed via a Chalk-Harrod mechanism, and the enantio-determining step was predicted to be oxidative addition of Si-H bond., (© 2021 Wiley-VCH GmbH.)