Herein we report the anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents under visible light. This approach serves as a safe and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux−Johnson reaction. A wide range of alkenes possessing oxidatively sensitive functionalities underwent anaerobic cleavage to generate carbonyl derivatives with high efficiency and regioselectivity. Mechanistic studies support that the transformation occurs via direct photoexcitation of the nitroarene followed by a nonstereospecific radical cycloaddition event with alkenes. This leads to 1,3,2-and 1,4,2-dioxazolidine intermediates that fragment to give the carbonyl products. A combination of radical clock experiments and in situ photoNMR spectroscopy revealed the identities of the key radical species and the putative aryl dioxazolidine intermediates, respectively.

A photoexcited-nitroarene-mediated anaerobic C−H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarene, which serves as the C−H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost-and atom-economical due to the commercial availability of the nitroarene, the sole mediator of the reaction. Because of the anaerobic conditions of the transformation, a noteworthy expansion in substrate scope can be obtained compared to prior reports. Mechanistic studies support that the photoexcited nitroarenes engage in successive hydrogen atom transfer and radical recombination events with hydrocarbons, leading to Narylhydroxylamine ether intermediates. Spontaneous fragmentation of these intermediates leads to the key oxygen atom transfer products.

Herein we report a visible light promoted method for the anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents. This approach serves as a safe and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux–Johnson reaction. A wide range of alkenes possessing oxidatively sensitive functionalities underwent anaerobic cleavage to generate carbonyl derivatives with high efficiency and regioselectivity. Mechanistic studies support that the transformation occurs via a solvent-separated ion-pair complex and the nitroarene is the sole photoabsorbing species. Direct photoexcitation of the nitroarenes empowers a radical cycloaddition event with alkenes leading to a 1,3,2-dioxazolidine intermediate, which fragments to give the carbonyl products. A combination of radical clock experiments and in situ PhotoNMR spectroscopy revealed the identities of the key radical species and the putative aryl 1,3,2-dioxazolidine intermediate, respectively.

A photoexcited nitroarene-mediated, anaerobic C–H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarenes, which serve as the C–H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost and atom economical due to the commercial availability of the nitroarene, the sole mediator of the reaction. Owing to the anaerobic conditions of the transformation, a noteworthy expansion in substrate scope can be obtained compared to prior reports. Mechanistic studies support that the photoexcited nitroarenes engage in successive hydrogen atom transfer and radical recombination events with hydrocarbons, leading to N-arylhydroxylamine ether intermediates. Spontaneous fragmentation of these intermediates leads to the key oxygen atom transfer products.

A photoexcited nitroarene-mediated, anaerobic C–H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarenes, which serve as the C–H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost and atom economical due to the commercial availability of the nitroarene, the sole mediator of the reaction. Owing to the anaerobic conditions of the transformation, a noteworthy expansion in substrate scope can be obtained compared to prior reports. Mechanistic studies support that the photoexcited nitroarenes engage in successive hydrogen atom transfer and radical recombination events with hydrocarbons, leading to N-arylhydroxylamine ether intermediates. Spontaneous fragmentation of these intermediates leads to the key oxygen atom transfer products.

Herein we report a visible light promoted method for the cleavage of alkenes into valuable carbonyl derivatives using economical nitroarenes as oxygen transfer reagents. This approach serves as an operationally simple and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux–Johnson reaction, with comparable efficiency and without their considerable limitations. Mechanistic studies support that the transformation occurs via a solvent separated ion-pair complex and that the nitroarene undergoes direct photoexcitation to trigger a radical cycloaddition event with alkenes leading to a 1,3,2-dioxazolidine intermediate that fragments to give the desired carbonyl products. A combination of radical clock experiments and in situ PhotoNMR spectroscopy revealed the identities of the key radical species and the putative aryl 1,3,2-dioxazolidine intermediate, respectively.

Herein we report the anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents under visible light. This approach serves as a safe and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux–Johnson reaction. A wide range of alkenes possessing oxidatively sensitive functionalities underwent anaerobic cleavage to generate carbonyl derivatives with high efficiency and regioselectivity. Mechanistic studies support that the transformation occurs via direct photoexcitation of the nitroarene followed by a non-stereospecific radical cycloaddition event with alkenes. This leads to 1,3,2- and 1,4,2-dioxazolidine intermediates that fragment to give the carbonyl products. A combination of radical clock experiments and in situ PhotoNMR spectroscopy revealed the identities of the key radical species and the putative aryl dioxazolidine intermediates, respectively.

Nickel-catalyzed, stereospecific cross-couplings via activation of secondary C–O bonds has been well developed in the past few years. Meanwhile, stereospecific cross-couplings of tertiary electrophiles have been rarely explored. Herein, we describe a nickel-catalyzed, ligand-free Suzuki-Miyaura vinylation, using easily prepared, highly enantioenriched tertiary benzylic carboxylates to install all-carbon quaternary stereocenters in high yields and ee’s. In addition to allowing stereospecific vinylation of these substrates for the first time, this method overcomes the longstanding requirement for a naphthyl group on the benzylic carboxylate<br>