The direct functionalization of C-H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon-carbon and carbon-heteroatom bonds. This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals

Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

The design and implementation of cascade reactions is a challenging facet of organic chemistry, yet one that can impart striking novelty, elegance, and efficiency to synthetic strategies. The application of cascade reactions to natural products synthesis represents a particularly demanding task, but the results can be both stunning and instructive. This Review highlights selected examples of cascade reactions in total synthesis, with particular emphasis on recent applications therein. The examples discussed herein illustrate the power of these processes in the construction of complex molecules and underscore their future potential in chemical synthesis.

Cascade reactions in total synthesis.

Over the last decade, substantial research has led to the introduction of an impressive number of efficient procedures which allow the selective construction of CC bonds by directly connecting two different CH bonds under oxidative conditions. Common to these methodologies is the generation of the reactive intermediates in situ by activation of both CH bonds. This strategy was introduced by the group of Li as cross-dehydrogenative coupling (CDC) and discloses waste-minimized synthetic alternatives to classic coupling procedures which rely on the use of prefunctionalized starting materials. This Review highlights the recent progress in the field of cross-dehydrogenative C sp 3C formations and provides a comprehensive overview on existing procedures and employed methodologies.

The Cross-Dehydrogenative Coupling of C sp 3H Bonds: A Versatile Strategy for CC Bond Formations

Reports that promote persulfate-based advanced oxidation process (AOP) as a viable alternative to hydrogen peroxide-based processes have been rapidly accumulating in recent water treatment literature. Various strategies to activate peroxide bonds in persulfate precursors have been proposed and the capacity to degrade a wide range of organic pollutants has been demonstrated. Compared to traditional AOPs in which hydroxyl radical serves as the main oxidant, persulfate-based AOPs have been claimed to involve different in situ generated oxidants such as sulfate radical and singlet oxygen as well as nonradical oxidation pathways. However, there exist controversial observations and interpretations around some of these claims, challenging robust scientific progress of this technology toward practical use. This Critical Review comparatively examines the activation mechanisms of peroxymonosulfate and peroxydisulfate and the formation pathways of oxidizing species. Properties of the main oxidizing species are scrutinized and the role of singlet oxygen is debated. In addition, the impacts of water parameters and constituents such as pH, background organic matter, halide, phosphate, and carbonate on persulfate-driven chemistry are discussed. The opportunity for niche applications is also presented, emphasizing the need for parallel efforts to remove currently prevalent knowledge roadblocks.

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Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks.

Electron-transfer processes: peroxydisulfate, a useful and versatile reagent in organic chemistry

Les constantes de vitesse pour l'addition du radical phenyle a des pyridines substituees en 4 protonees ou non sont determinees par competition avec l'abstraction de chlore a partir de CCl 4 . A partir de ces constantes de vitesse, l'utilisation du radical phenyle a partir de sel de diazonium ou du peroxyde de benzoyle pour generer des radicaux alkyles par enlevement d'iode ou d'hydrogene a ete developpee en tant que procede general d'alkylation de bases heteroaromatiques

Polar effects in free-radical reactions. Rate constants in phenylation and new methods of selective alkylation of heteroaromatic bases.

Polar effects in free-radical reactions. New synthetic developments in the functionalization of heteroaromatic bases by nucleophilic radicals

Les substitutions des pyridine, quinaldine, lepidine et cyano-3 et -4 pyridines protonees par les radicaux Ph, Me, n-Pr, i-Pr, t-Bu, α-tetrahydrofuryle, dioxannyle et benzyle sont modifiees selon la nature du solvant

Polar effects in free-radical reactions. Solvent and isotope effects and effects of base catalysis on the regio- and chemoselectivity of the substitution of protonated heteroaromatic bases by nucleophilic carbon-centered radicals

Claudio Giordano

Papers

Electron-transfer processes: peroxydisulfate, a useful and versatile reagent in organic chemistry

Polar effects in free-radical reactions. Rate constants in phenylation and new methods of selective alkylation of heteroaromatic bases.

Polar effects in free-radical reactions. New synthetic developments in the functionalization of heteroaromatic bases by nucleophilic radicals

Polar effects in free-radical reactions. Solvent and isotope effects and effects of base catalysis on the regio- and chemoselectivity of the substitution of protonated heteroaromatic bases by nucleophilic carbon-centered radicals

Synthesis of Anti-Inflammatory α-Arylalkanoic Acids by 1,2-Aryl Shift. New Synthetic Methods (42)