ConspectusThe selective oxidation of organic molecules is a fundamentally important component of modern synthetic chemistry. In the past decades, direct oxidative C–H and C–C bond functionalization has proved to be one of the most efficient and straightforward methods to synthesize complex products from simple and readily available starting materials. Among these oxidative processes, the use of molecular oxygen as a green and sustainable oxidant has attracted considerable attention because of its highly atom-economical, abundant, and environmentally friendly characteristics. The development of new protocols using molecular oxygen as an ideal oxidant is highly desirable in oxidation chemistry. More importantly, the oxygenation reaction of simple molecules using molecular oxygen as the oxygen source offers one of the most ideal processes for the construction of O-containing compounds. Aerobic oxidation and oxygenation by enzymes, such as monooxygenase, tyrosinase, and dopamine β-monooxygenase, have been obs...

Oxygenation via C–H/C–C Bond Activation with Molecular Oxygen

In recent years, radical C–C bond cleavage reactions have been increasingly understood and used to perform transformations that complement traditional ionic processes. However, to date radical C–C bond cleavage/functionalization reactions have not been the subject of a dedicated review. Herein we summarize the most recent and significant developments in the radical activation and functionalization of carbon–carbon bonds, with an emphasis on both synthetic outcomes and reaction mechanisms, and highlight how these radical C–C bond cleavage reactions enable challenging transformations.

Cleavage of carbon-carbon bonds by radical reactions.

This review is an update on tris(trimethylsilyl)silane, TTMSS, in organic chemistry, focusing on the advancements of the past decade. The overview includes a wide range of chemical processes and synthetic strategies under different experimental conditions, including functional group insertion and transformations, as well as preparation of complex molecules, natural products, polymers, surfaces, and new materials. These results reveal how TTMSS has matured over the past 30 years, and they further establish its value as a free radical reagent with widespread academic and industrial applications.

Thirty Years of (TMS)3SiH: A Milestone in Radical-Based Synthetic Chemistry.

Biomass is renewable and the most abundant carbon resource, and it shows great potential for sustainable production of chemicals in the future With respect to limited fossil reserves, biomass conv

Sustainable Productions of Organic Acids and Their Derivatives from Biomass via Selective Oxidative Cleavage of C-C bond

Controlling selectivity is of central importance to radical chemistry. However, the highly reactive and unstable radical intermediates make this task especially challenging. Herein, a strategy for taming radical redox reactions has been developed, in which solvent-bonding can alter the reactivity of the generated radical intermediates and thereby drastically alter the reaction selectivity at room temperature. Various β-oxy sulfoxides and β-hydroxy sulfides can be facilely obtained, some of which are difficult to synthesize by existing methods. Notably, neither a metal catalyst nor any further additives are necessary in these processes.

Solvent-Enabled Radical Selectivities: Controlled Syntheses of Sulfoxides and Sulfides

Copper-Catalyzed Aerobic Oxidative C–C Bond Cleavage of Unstrained Ketones with Air and Amines

Iodine-Catalyzed Oxidative Functionalization of Azaarenes with Benzylic C(sp3)–H Bonds via N-Alkylation/Amidation Cascade: Two-Step Synthesis of Isoindolo[2,1-b]isoquinolin-7(5H)-one

An alternative thioesterification reaction via copper-catalyzed oxidative coupling of readily available aroylhydrazides with disulfides is developed, in which oxidative expulsion of N2 overcomes the activation barrier between the carboxylic acid derivatives and the products. The reaction produces various thioesters in good to excellent yields with good functional group tolerance. In the reaction, stable and easily available aroylhydrazides are used as acyl sources and the relatively odorless disulfides are used as S sources. Mechanistic investigations demonstrate that the reaction of copper salt and oxidant (NH4)2S2O8 allows for achievement of tandem processes, including deprotonation, free-radical-mediated denitrogenation, and C-S bond formation.

Cu-Catalyzed Oxidative Thioesterification of Aroylhydrazides with Disulfides.

Efficient 4,5-dihydro-1H-imidazol-5-one formation from amidines and ketones under transition-metal free conditions

From Simple to Complex: Rhodium(III)-Catalyzed C-C Bond Cleavage and C-H Bond Functionalization for the Synthesis of 3a,8b-Dihydro-1H-cyclopenta[b]benzofuran-1-ones.

Wang Zhou

Papers

Copper-Catalyzed Aerobic Oxidative C–C Bond Cleavage of Unstrained Ketones with Air and Amines

Iodine-Catalyzed Oxidative Functionalization of Azaarenes with Benzylic C(sp3)–H Bonds via N-Alkylation/Amidation Cascade: Two-Step Synthesis of Isoindolo[2,1-b]isoquinolin-7(5H)-one

Cu-Catalyzed Oxidative Thioesterification of Aroylhydrazides with Disulfides.

Efficient 4,5-dihydro-1H-imidazol-5-one formation from amidines and ketones under transition-metal free conditions

From Simple to Complex: Rhodium(III)-Catalyzed C-C Bond Cleavage and C-H Bond Functionalization for the Synthesis of 3a,8b-Dihydro-1H-cyclopenta[b]benzofuran-1-ones.