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

The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C–C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of...

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Good Partnership between Sulfur and Fluorine: Sulfur-Based Fluorination and Fluoroalkylation Reagents for Organic Synthesis

Oxidative Coupling between Two Hydrocarbons: An Update of Recent C–H Functionalizations

Carbon trifluoromethylation reactions of hydrocarbon derivatives and heteroarenes.

Molecular Iodine Catalyzed Cross-Dehydrogenative Coupling Reaction between Two sp3 C–H Bonds Using Hydrogen Peroxide

We report the visible-light-induced trifluoromethylation of arenes and heteroarenes using sodium trifluoromethanesulfinate catalyzed by anthraquinone-2-carboxylic acid. This reaction is a metal-free trifluoromethylation of arenes and heteroarenes catalyzed by a photoredox organocatalyst. Perfluoroalkylated arenes were also produced using sodium perfluoroalkylsulfinates.

Metal-Free Direct CH Perfluoroalkylation of Arenes and Heteroarenes Using a Photoredox Organocatalyst

Oligosaccharide synthesis on a fluorous support

Fluorous Oligosaccharide Synthesis Using a Novel Fluorous Protective Group

The synthesis of β-hydroxy sulfones from alkenes and sodium sulfinates under aerobic oxidative conditions was achieved in the presence of a catalytic amount of molecular iodine. Molecular oxygen in air serves as the terminal oxidant and the catalytic amount of molecular iodine acts as the sulfonyl radical initiator and peroxide reductant.

Tsuyoshi Miura

Papers

Molecular Iodine Catalyzed Cross-Dehydrogenative Coupling Reaction between Two sp3 C–H Bonds Using Hydrogen Peroxide

Metal-Free Direct CH Perfluoroalkylation of Arenes and Heteroarenes Using a Photoredox Organocatalyst

Oligosaccharide synthesis on a fluorous support

Fluorous Oligosaccharide Synthesis Using a Novel Fluorous Protective Group

Molecular-iodine-catalyzed aerobic oxidative synthesis of β-hydroxy sulfones from alkenes